Methods, Compositions and Articles for Olfactory-Active Substances

ABSTRACT

The present invention is directed to methods, compositions and articles comprising olfactory-active compositions. An article of the present invention comprises a structural component and an olfactory-active composition. The article may control the release, release rate or absorption of the olfactory-active composition. The article may be of various shapes and sizes. A method of use of an article comprises providing fragrance to an environment.

RELATED APPLICATIONS

The present application claims the priority of U.S. Provisional PatentApplication Ser. Nos. 61/319, 431, filed Mar. 31, 2010; 61/409, 627,filed Nov. 3, 2010; and 61/419,959, filed Dec. 6, 2010; each of which isincorporated herein in its entirety.

TECHNICAL FIELD

The various embodiments of the present invention relate generally toarticles that provide olfactory-active substances, such as an articlethat provides odorous compounds, for example, a fragrance, and methodsand compositions for making and using such articles.

BACKGROUND OF THE INVENTION

It has become a desired accessory for homes, automobiles and otherspaces to provide a scented environment. Materials such as ceramics,polymers, wood and cellulose materials have been used to release afragrance. Cotton has been used to release volatile materials, such as afragrance, and examples are described in U.S. Pat. Nos. 2,615,754 and5,372,303. Fabric has also been used as an absorbent medium from which avolatile material can evaporate as described in U.S. Pat. No. 2,626,833.In U.S. Pat. No. 855,984 a sponge is used to volatilize a perfume ordisinfectant. U.S. Pat. No. 1,988,141 describes the use of a felt pad torelease a perfume. These and similar articles have a very rapid releaseof fragrance from their matrix, and do not provide a prolonged releaseof fragrance.

Wood has been used to hold scent, for example, incense sticks. Torelease significant quantities of the scent, the wooden incense sticksare burned and the aroma is released into the environment. Allowing theincense sticks to release their scent without burning results in aninadequate scent release. Wood is not highly absorbent and thereforeabsorbs low amounts of scented material. Wood pulp has been used toabsorb fragrance and release it, as described in U.S. Pat. No.2,120,204. The use of wood pulp may pose problems when it is friable andcannot be made into stable articles.

Wood sticks or reeds, without a fragrance applied initially, have beenused in reed diffusers. In a reed diffuser, the wood, such as two orthree bamboo reeds, are placed in a container holding a scented oil. Theoil wicks up the central portion of the reed and the fragrancevolatilizes out the upper end of the reed. The reeds must be turnedfrequently so that the previously immersed end of the reed is exposed tothe air outside the container. Often the reeds clog from debris orbiocontaminants in the oil, and are not effective at providing long-termfragrance to an environment.

What is needed are articles that provide olfactory-active substances,and methods for making and using such articles, and compositions usedfor articles that provide olfactory-active substances, such asfragrance, to an environment, including articles that are durable,easily manufactured and provide a slow or controlled rate of release ofthe olfactory substance, such as fragrance, for many applications.

SUMMARY

The present invention is directed to methods and compositions for anarticle that provides an olfactory-active substance, such as afragrance, to an environment and to methods for making and using such anarticle. An aspect of the invention comprises an article comprising astructural component and at least one olfactory-active substance. Astructural component comprises a matrix material that is an absorbentmaterial. In an article, the matrix material absorbs or adsorbs the atleast one olfactory-active substance. The matrix material may haveadditives incorporated into the matrix material. A structural componentmay have at least a portion of the surface of the structural componentcovered or overlaid by a coating or a barrier. The coating or barriermay aid in the controlled release of the olfactory-active substance fromstructural component, and may extend the length of time that theolfactory-active substance is released from an article.

FIGURES

FIG. 1 is a drawing of an example of an article of the presentinvention.

FIG. 2 is a drawing of an example of an article of the presentinvention.

FIG. 3 is a graph of release of nC12 from a structural component, wherethe y axis is wt loss in grams and the x axis is time in hours.

FIG. 4 is a graph of release from coated and non-coated structuralcomponents, where the y axis is wt loss in grams and the x axis is timein hours.

FIG. 5 is a graph of release from coated and non-coated structuralcomponents, where the y axis is wt loss in grams and the x axis is timein hours.

FIG. 6A is a graphs of release from structural components with differingmatrix materials, and FIG. 6B is a graph of release from a structuralcomponent, where the y axis is wt loss in grams and the x axis is timein hours.

FIG. 7A is a graph of release from coated structural components, andFIG. 7B is a graph of release from coated and uncoated structuralcomponents, where the y axis is wt loss in grams and the x axis is timein hours.

DETAILED DESCRIPTION

The present invention comprises articles, methods and compositions thatprovide an olfactory-active substance, such as a fragrance, to anenvironment. The present invention comprises methods and compositionsfor articles that provide one or more olfactory-active substances, forexample, fragrances, to an environment. An article of the presentinvention may comprise one or more olfactory-active substances, such asfragrance, contained in a portable, free-standing structural component.An article may be two-dimensional with varying shapes and sizes, such asflat sheet embodiments, or an article may be three-dimensional withvarying shapes and sizes, such as a desired shape, a solid rod, a rodwith a core, a rod with two cores, a rod with a honeycomb structure, asolid sphere, a hollow sphere, or any other geometric shape, or otherpossible arrangements.

An article may be provided individually or in groups of two or more, andmay be held in a receptacle having apertures to allow the passage offragrance molecules. An article may be provided in any shape, forexample, as a rod or a shaped rod, such as by crimping or bending a rod,or may be assembled from a combination of articles, such as placingseveral small rods, each held with another rod by a holder and thearticles so held provide a shape. An article may optionally furthercomprise dyes, coating compositions, holder elements or attachmentelements.

An article of the present invention comprises a structural componentwhich is made from a matrix material composition, and anolfactory-active substance. A structural component may be coated, dyed,or further treated in forming an article of the present invention.

The present invention comprises compositions used in making an article.A structural component may comprise one or more matrix materialcompositions. A matrix material composition may comprise natural andsynthetic pulp compositions, or pulp compositions combined with otherproducts, including but not limited to paper, cellulose, celluloseacetate, pulp lap, cotton lintners, biological plant-derived materials(from living plants), synthesized pulp compositions, and mixed pulps. Amatrix material composition may comprise additives, materials thatprovide strength, rigidity or structure to a matrix materialcomposition. For example, a composition may comprise nanomaterials asadditives. An article of the present invention may be referred to as apulp article, indicating that the article comprises a matrix materialcomposition which was made from a pulp composition of the presentinvention.

The present invention comprises methods of making the compositions,methods of making articles comprising compositions, and methods of usingan article.

A matrix material composition may comprise pulp. As used herein, and asknown in the art, pulp is primarily a collection of fibers with othercomponents of the source material, wherein the fibers are derived from anatural or synthetic source material, for example, biological plants(natural) or petroleum-based synthesis products (synthetic). The pulpcomposition may have a moisture content. Pulp and pulp composition areused interchangeably herein. Basic steps in pulp making are well knownin the art and comprise converting plant fiber or other fibers into ausable form such as chips, converting chips into fibers or pulp,optionally treating the pulp such as bleaching the pulp, washing thepulp, and forming a pulp composition. Pulp may be produced from varioustypes of woods using any one of several pulping techniques. The pulp maybe from hardwoods, softwoods, or mixtures thereof. Suitable hardwoodsinclude, but are not limited to, aspen, birch, cottonwood, poplar,maple, and the like, and mixtures thereof. Suitable softwoods include,but are not limited to, pine (e.g., red pine, jack pine, and Southernyellow pine), spruce, balsam fir, Douglas fir, and the like, andmixtures thereof. The pulp may be a mixed-blend of wood from variousspecies of hardwood, deciduous trees including, but not limited to, ash,aspen, beech, basswood, birch, black cherry, black walnut, butternut,buckeye, chestnut, cottonwood, dogwood, elm, eucalyptus, gmelina,hackberry, hickory, holly, locust, magnolia, maple, oak, poplar, redalder, redbud, royal paulownia, sassafras, sweetgum, sycamore, tupelo,willow, yellow-poplar, and combinations thereof. The pulp may comprisewood from various varieties of trees within the species of trees. It iscontemplated that other species of hardwood or deciduous trees may beused. It is also contemplated that a single species of hardwood ordeciduous trees may be used.

The pulp may comprise non-wood fibers including, but not limited to,bagasse, straw, kenaf, grasses, hemp, and combinations thereof. It iscontemplated that pulp may comprise wood from hardwood or deciduoustrees in combination with non-wood fibers.

Pulp may be made from recycled materials, and comprises recovering wastepaper and remaking it into new products. Three categories of paper thatcan be used as feedstocks for making recycled paper are mill broke,pre-consumer waste, and post-consumer waste. Mill broke is papertrimmings and other paper scrap from the manufacture of paper.Pre-consumer waste is material which left the paper mill, which has beendiscarded before it was ready for consumer use. Post-consumer waste ismaterial discarded after consumer use, such as old magazines, oldnewspapers, office waste, old telephone directories, and residentialmixed paper. Paper suitable for recycling is called scrap paper.Feedstocks for pulp may comprise a range of about 100% scrap paper to0.001% scrap paper, and may comprise mixed pulp compositions comprisingvirgin fibers and recycled fibers. Deinking processes may be used withrecycled materials.

Methods for making pulp include (i) chemical, (ii) mechanical, (iii)thermal, and (iv) combinatorial methods. Industrial alkaline chemicalpulping processes include the Kraft (or sulfate), soda, and alkalinesulfite processes. The Stone GroundWood (SGW) process involves makingpulp by pressing logs and chips against an abrasive rotating surface.Another type of mechanical pulping is Refiner Mechanical Pulp (RMP)featuring atmospheric refining with no pre-treatment of wood chips.

Thermo Mechanical Pulping (TMP) is a mechanical pulping process thatevolved from RMP and a high temperature process known as the Apslundprocess. Thermo Refiner Mechanical Pulping (TRMP) is a variation inThermo Mechanical Pulping. In this case, the chips are preheated underpressure and refining is carried out at atmospheric pressure.

Other pulping methods include chemical treatment with thermo-mechanicalpulping (CTMP), chemi-mechanical pulping (CMP), and the chemicalpulping, sulfate (kraft) or sulfite processes. Pulps may be treated, forexample to lighten the color of the pulp. Bleaching may use chemicalproducts to dissolve and extract part of the lignin, or to discolor it.These chemical products include chlorine dioxide, hydrogen peroxide andozone for chemical pulps, and hydrogen peroxide for mechanical pulps.

Electron beam processing or electron processing technology (EPT) ofchemical wood pulp can be used to control pulp viscosity or degree ofpolymerization.

It may be desirable to generate pulps with lower overall lignin content,or no lignin content, as these pulps require less bleaching chemicals,react less with fragrances, and generate fewer pollutants, especiallyabsorbable organic halides (AOX). Cellulose pulps having a high lignincontent are referred to as “high-yield pulps,” and this class of pulpsincludes groundwood pulps, chip-refined pulps, thermo-mechanical pulps,chemi-mechanical pulps, and semi-mechanical pulps. The fibers of thelignocellulosic material are freed at least in part mechanically andoptionally also in part chemically. The mechanical defibration iseffected in a grinder, a disc refiner or a screw defibrating apparatus,in which the pulp is subjected to a mild mechanical shearing forcewithout appreciably lowering its resistance to dewatering. Fibrillationmay be used increase the flexibility of the fibers and bring about thefine material characteristics of quality processed pulp.

Methods of the present invention comprise forming an article of thepresent invention having a structural component comprising a pulp matrixmaterial. An example of a method for making a matrix material comprisesforming a sheet of paper from pulp. After the wood chips are digestedand optionally, the resultant fibers bleached, the fibers are formedinto a wet-laid pulp mat. In this operation, the fibers enter a headboxwhere they are mixed with water and any chemicals or other materialsthat are added to the pulp. The fibers exit the headbox onto a movingscreen, known as a wire through which the water in the web is drainedboth by gravity and by vacuum. This step, known in its initial stage asformation, is usually accomplished by passing an aqueous dispersion of alow concentration of pulp (e.g., 0.5% to 1% by weight solids is typical)over the wire. This wire, assisted in certain situations by vacuum orsuction, increases the consistency of the mat or web to approximately 20to 35 weight percent solids.

The mat or web is then compressed or squeezed in a “press section” toremove additional water. This is usually accomplished by felt presses, aseries of rollers each having a felted band for contact with the mat orweb. These presses remove additional free water and some capillarywater, thus resulting in an increase in consistency of the mat or web toa range of about 30 to 60 weight percent. More or less pressing may beapplied, depending on the desired product.

Following the press section, the pulp sheet is then dried in a dryersection. In the drier section, the remaining water content of the pulpsheet is reduced to obtain a pulp consistency which typically rangesbetween about 88 to 97 weight percent (3 to 12 weight percent moisture),more usually between 90 to 94 weight percent (6 to 10 weight percentmoisture). The wet-laid cellulose pulp fibers form into a sheet andattach to each other at contact points by hydrogen bonds. This processis called wet forming.

Other methods of making pulp matrix material are known. For example, inthe Fourdrinier process, a pulp matrix material is generally produced byforming a fiber mat from aqueous cellulosic slurry on a wire screen.Methods generally comprise a head box having a flow chamber upstreamfrom the wire screen. The head box receives the aqueous cellulosicslurry and deposits the slurry onto the wire screen where a paper mat isformed. The paper mat is removed from the wire screen and furtherprocessed, including drying, to form article matrix material. Dry or wetlap processes may also be used to form pulp matrix materials.

Commercial pulps may be available in sheet form. In order to facilitatethe blending of the fibers with a polymeric material, the fiber sheetsmay be broken down to individual fibers or small aggregates of fibers.The step of granulating may be performed using a rotary knife cutter tobreak up the pulp material. The granulation process may reduce thelength of the fibers. A reduction in fiber length may decrease thereinforcing impact of a fiber additive.

Porosity of a matrix material may be controlled by the compactness ofthe fibers. Porosity of a pulp or an article of the present inventionmay be controlled or altered in various ways. The compactness of thefibers affects the degree in which the matrix material allows gas orliquid to pass through it. The matrix material porosity may affect otherproperties of the matrix material or the article made with such a matrixmaterial, and changes in porosity may effect changes in othercharacteristics of the article. For example, porosity may affect uptakeor load amount of olfactory-active substances, or may affect the rate ofrelease of olfactory-active substances. Porosity of the matrix materialmay be affected by adding other materials, such as additives, to thepulp, as the matrix material is being formed from a pulp composition, orto a structural component made from a matrix material.

The nature of a pulp matrix material is such that the bonding of pulpfibers produces many tiny air passages throughout the pulp matrixmaterial, which can either be completely submerged in the matrixmaterial of a structural component, extend from the surface down intothe interior of the structural component of an article, or penetratecompletely through the structural component of an article. The porosityof a pulp matrix material may be affected at any stage of the pulpmatrix material production process. An increased level of fiber refiningcauses the fibers to bond together more strongly and tightly, making thepulp matrix material denser, reducing the network of air passages andthe porosity. Surface sizing, coating, calendering or supercalenderingmay seal and/or compress surface fibers, reducing the porosity of thestructural component.

Porosity may affect how completely and how quickly additives,olfactory-active compositions or other liquids are absorbed into a pulpmatrix material, such absorption may occur primarily by capillaryaction. Pulp matrix material with high porosity may have increasedadditive absorbency.

Porosity of a pulp matrix material is measured quantitatively as eitherthe length of time it takes for a quantity of air to pass through asample, or the rate of the passage of air through a sample, using eithera Gurley densometer (in the first case) or a Sheffield porosimeter (inthe second case).

Porosity of a matrix material, a structural component or an article, maybe increased or decreased by the addition of additives. Additives may beadded to pulp during the pulp making process, during formation of thematrix material, during formation of the structural component from amatrix material, or at steps when an article is formed. For example,additives can be provided to pulp that are space-filling additives tomake a matrix material having space-filling additives. An article isformed with a structural component made from the matrix material withspace-filling additives and then is treated in such a way that thespace-filling additive is destroyed or reduced in size, leaving openingsor pores in the matrix material of the article, and increasing itsporosity.

The overall porosity of an article may be decreased by treating at leasta portion of the surface of a structural component of an article. Theporosity of an article may be affected by reducing the porosity of thematrix material, reducing the porosity of the structural component, suchas by coating or treating a portion of a surface of the structuralcomponent, or by coating or treating a portion of the article.Conversely, the porosity of an article may be increased.

Cellulosic matrix materials may be formed that have pores, gaps, orchannels similar to those found in a flexible sponge. Such matrixmaterials may have functional groups, such as ion-exchange groups,chemically bonded to the cellulose. In a method, as described in GB914421, a pre-formed flexible cellulosic sponge is modified by reactionwith a reagent which introduces ion-exchange groups, such asorthophosphoric acid or sodium chloroacetate. GB 1387265 disclosesion-exchange cellulosic material prepared by reaction of cellulose witha reagent which introduces ion-exchange groups, followed by regenerationinto the desired physical form, among which is sponge. GB 1226448discloses a method of making an ion exchanger, which comprises theintroduction of cross-linking residues into regenerated cellulosetogether with or followed by introduction of cation or anion exchangegroups into the cellulose. The cellulose may be obtained from viscose.The cellulose may be used in a variety of physical forms such as rod,filament, yarn, woven cloth, flakes, beads, granules, powder, sponge,tube or sheet.

A matrix material of the present invention may comprise primary andsecondary pores. The primary pores are interconnecting pores which aredimensioned so as to allow the free passage of liquids or gasesthroughout the matrix material. The secondary pores are provided in thewalls of the primary pores. The rate of transport of liquids or gases inand out of the pores may be rapid or slow.

The production of a porous matrix material comprising interconnectingpores generally involves contacting a solution of the matrix material,such as a polymeric material, with a pore-forming agent such as a gas.Where the polymeric material is cellulose, the polymeric material iscontacted with the gas either prior to, or simultaneous with, generationof the porous material. A gas or gas forming materials are introducedinto the polymeric solution. Examples of gas-forming materials includesolids, volatile liquids, chemical reagents, such as calcium carbonateand acid, thermally decomposable materials which will cause evolution ofa gas by, for example, decomposition of bicarbonate, or biologicalagents, such as dextrose and yeast.

Gas-forming materials may be solid reagents such as powders, crystals,oils, waxes or ground biological tissue. The use of solids as precursorsfor the gaseous pore-forming agents may be suitable for the productionof primary pores. A gas-forming reagent may be removed after or duringthe regeneration of the cellulose into solid form, the removal typicallyinvolving either treatment with an acid, an alkali, or an enzyme, theuse of electromagnetic energy or solvent action.

A method of producing a porous matrix material having an interconnectingporous structure involves use of a xanthate. The size of pores producedby gas given off by the xanthate can be varied by varying the degree ofsubstitution of the xanthate.

A method of producing a porous matrix material having an interconnectingporous structure involves the use of crystals of hydrated sodium sulfatewhere particles of varying sizes can again be used. Crystals of hydratedsodium sulfate having a particle size in the range from 200 to 400microns can be used to make the interconnecting pores. Crystals ofhydrated sodium sulfate having a particle size of 1500 to 3000 micronscan be used. For pore sizes in the order of 100 microns other solidssuch as calcium carbonate may be used.

The actual volume of the primary pores (i.e., fractional voidage) isdependent on the amount of primary-pore forming agent introduced intothe porous matrix material polymeric solution and may take any value upto 95% of the total void volume.

The thickness of the walls of the primary pores may depend on thequantity of primary pore forming agent which is mixed with the solutionof porous matrix material polymeric material. Among other factors, theminimum wall thickness may depend on how closely the particles of theprimary pore forming agent fit together. The overall amount offunctional groups which can be introduced per unit volume into theporous matrix material will generally be increased as the density of theporous matrix material is increased. The thickness of the primary porewalls may be varied depending on the article to be made from the porousmatrix material. It may not be possible to obtain uniform wallthicknesses within a porous matrix material. For example, a cellulosicporous matrix material may have a wall thickness ranging between 5 and45 microns.

The secondary pores may be naturally occurring in the polymer as aresult of variation in its density or may be formed by the use of a poreforming agent or agents which are generally used in conjunction with theprimary pore forming agent. Typically the secondary pores are smallerthan the primary pores and may be formed by any of the followingmethods.

A solution of the polymeric material may be mixed with a removablereagent having individual particles of a predetermined size, so as toproduce a porous matrix material having a desired secondary porestructure (i.e., a structure having a pore size determined by thereagent particle size). A liquid (probably immiscible with the polymersolution) can be added to the polymer solution which upon mixing formscontinual channels within the liquid polymer. Alternatively, the densityof the polymer solution, such as cellulose, may be lowered by theaddition of a suitable solvent so that when the cellulose isregenerated, the resulting sponge has an open pore structure. Suitablemethods of removing the added gas or liquid are known. Secondary poresmay be produced by contacting the polymer solution with a solidpore-forming agent.

It is recognized that the nature of a porous matrix material, includingthe general porous structure, may depend on a wide range of factorswhich influence the manufacturing system. For example, changes may bemade to the concentration, degree of polymerization, or viscosity of thepolymer. Agents, such as surfactants, likely to effect the secondary andprimary pore structure may be added.

The porous matrix material may be used in accordance with the presentinvention to form a structural component of an article as describedherein and which may be in the form of a block, an annulus, a continuoussheet, a rolled sheet, a disc, a tape, a rod, a pad, or otherthree-dimensional form, or the like.

A matrix material comprising lintners, including but not limited to,cotton, lotka or abaca, is contemplated by the present invention. Thelintners may comprise from 0.1% to 99.9% by weight of the total weightof the matrix material. A matrix material comprising a synthetic pulp isalso contemplated by the present invention. For example, U.S. Pat. No.3,770,856 discloses the production of fine fibrous structures byflashing an aqueous emulsion containing a polymer and solvent from ahigher pressure and temperature zone to a lower pressure and temperaturezone. The resulting structure is macerated in a mixer whereby obtainedare fine flat fibers in a fibrillar state of an average width of from 5to 10 microns and length of from 3 to 5 mm. The resulting fibers can bepressed or molded to form a matrix material for use in a structuralcomponent.

Extruded synthetic pulp compositions are used to form matrix materialsof the present invention. British Pat. No. 1,221,488 discloses a processfor the production of yarn which involves extruding a blend ofpolyethylene and blowing agent so as to produce an extrudate of foamedpolyethylene. The latter is drawn so that it becomes orientatedessentially in the direction of extrusion. The drawn foamed polyethyleneis subjected to forces such that the walls of the foam are broken down.The resulting extrudate is a three-dimensional structure ofinterconnected fiber elements which comprise a matrix material. U.S.Pat. No. 3,634,564 discloses a process for the manufacture offibrillated foamed films involving mixing a thermoplastic polymer with ablowing agent and extruding the mixture into a foamed polymer film andthereafter stretching the foamed film uniaxially. The stretching at anelevated temperature causes the voids of the foam to split. These fibersmay be formed, pressed, molded, melted, partially melted or treated inknown methods to form matrix materials for use as structural components.

In some cases, the extrudate is orientated. Orientation refers to aprocess wherein the crystalline structure in polymeric materials areplaced in alignment so as to produce a highly uniform structure. It isbelieved that orientation causes the axes of the molecules of thepolymer to more generally line up in the same direction. Generallyorientation is obtained by stretching (or pulling) the polymer while itstemperature is below its melting point but above its transitiontemperature. The present invention contemplates extrudates that are notdrawn or oriented and the resulting fibers may or may not be oriented ina matrix material.

U.S. Pat. No. 3,954,928 discloses a process for the preparation offibrillated extrudate by extruding a molten thermoplastic resincontaining a foaming substance through a die. The extrudate is quenchedalmost as it leaves the die to a temperature below the resin's glasstransition temperature. The resin can be a blend of polystyrene and apolyolefin, e.g., polyethylene, but the latter is present in an amountof at most 40% and preferably 30% or less by weight based on the blend.

U.S. Pat. No. 4,210,487 discloses that a polyolefin by itself can beprocessed to fibers suitable for blending with cellulosic pulp to form amatrix material. A mixture of polystyrene and polyethylene orpolypropylene in which the mixture contains more than 40 weight % of thepolyolefin is equally suitable for blending with cellulosic pulps. U.S.Pat. No. 4,210,487 further discloses a process of preparing a syntheticpulp composition from a synthetic thermoplastic, fiber-forming polymer.The resin is extruded along with a blowing agent to form material havinginterconnected fibrils and fibers. The material is attenuated as itleaves the extruder die to induce formation of fibers and fibrils. Theattenuation occurs while the polymer is in a molten or amorphous state.The resulting fibrillated material is then subjected to a cutting and/orshearing action which results in the foamed material breaking down intosmall short fibers having many attached fibrils. This synthetic fibrousmaterial readily mixes with cellulosic pulp to allow preparation of apaper sheet having varying amounts of the desired synthetic polymer. Theresulting paper, depending on the particular polymer and the amount canhave properties superior to that of paper of only cellulosic pulp. Thesynthetic thermoplastic polymer is selected from the group consisting ofpolypropylene, polyethylene or a mixture of polystyrene andpolypropylene or polyethylene in which the mixture contains more than 40percent by weight of the polyolefin.

The present invention comprises compositions comprising additives. Oneor more additives may be added to a matrix material composition, such asa pulp. Pulps may comprise additives that are added during production ofthe pulp, and/or during formation of a matrix material, or duringformation of a structural component of an article, to confer one or morespecial characteristics. For example, the addition of mineral fillerssuch as kaolin, titanium oxide, talc, calcium carbonate, may aid inprintability, opaqueness and dimensional stability of matrix materialand/or a structural component. Additives may be incorporated in a pulpcomposition, in the matrix material of an article as it is being formed,in the article after formation or in an olfactory-active substancecomposition.

An example of an additive is a starch. Starch compounds may be added inthe matrix material itself, or may be used to adhere one layer of apaper matrix material to another layer of paper in a rolling process toproduce a structuralcomponent comprising a rolled continuous paper rod.The starch compounds may be used as control release elements. Bothnatural unmodified starch and modified starch can be used. Any starchappropriate for use in papermaking may be used including but not limitedto, dextrin, as well as combinations of starch types, dextrin types andcombinations of starches and dextrins. Also, maltodextrins and otherforms of carbohydrates can be used as the starch component. Unmodifiedstarch is a commodity chemical produced from the root, stem or fruitfrom a number of plants. It is a high molecular weight carbohydratepolymer which is comprised of linear and branched polysaccharidepolymers and it may have a moisture content from about 8% to about 20%,most commonly from about 11% to about 13%. Starches such as thosederived from corn, wheat, barley, tapioca, rice, potato and/or othersuitable plant source, and the like can be used, as well as hybrids.Blends of starches from various sources also can be used. Pearl starchesand powdered starches may be used.

Modified starch can be mechanically, chemically or heat modified.Modified starches have different properties than unmodified starch,including differences in solubility, film forming, whiteness, gelstrength, viscosity stability, adhesivity, resistance to shear andresistance to freeze-thaw degradation. Starches derived from othergenetic forms of corn, such as high amylose and waxy corn, as well assorghum varieties, would also be suitable. Chemically modified starchesinclude modified oxidized starch such as hypochlorite-oxidized starch,acid thinned starches, cross-bonded starch, etherified starches,esterified-starches and others which have reduced molecular weight, highfluidity and/or functional subgroups. Examples of chemically modifiedstarches that are commercially available are SUREBOND™, Industrial CornStarch, or STABLEBOND™. Industrial Corn Starch available from CornProducts. FOXHEAD™. Cationic Starches are available from Corn Productsand Corn Products' oxidized starch.

Additives may comprise nanofibers. Nanofiber is a broad phrase generallyreferring to a fiber with a diameter less than 1 micron. Examplesinclude, but are not limited to, glass fibers in the sub-micron range,polymeric meltblown fibers, 0.25 micron diameter electrospun nanofiberscommercially available nanofibers and nanofiber webs.

Nanofibers may be organic or inorganic materials including, but notlimited to, polymers, engineered resins, ceramics, cellulose, rayon,glass, metal, activated alumina, carbon or activated carbon, silica,zeolites, or combinations thereof. Combinations of organic and inorganicfibers and/or whiskers are contemplated and within the scope of theinvention as for example, glass, ceramic, or metal fibers and polymericfibers may be used together.

Nanofibers, comprising nanofibers or microfibrils made from cellulose,may be added to a pulp composition used as a matrix material of thepresent invention. A plant cell wall is in part stiffened by cellulosemicrofibrils. In general, cellulose fibers are 30 mm wide and about 2-3mm long, and are made of nanometer scale microfibrils which aretypically 4 nm wide and about 100-200 nm long. As used herein“microfibrillated cellulose” or “cellulose nanofibers” or cellulosemicrofibrils are used interchangeably and are understood by thoseskilled in the art to mean very small fibers derived from cellulose.Microfibrillated cellulose (MCF) is isolated and purified cellulosefibers recovered from a cellulose source in a process which results incellulose filamentous structures that are nanoscale size.

MCF was developed in the 1980s and is a form of expanded high-volumecellulose, moderately degraded and greatly expanded in surface areasthat may be obtained by a homogenization process. MCF nanofibers may beused to add strength and other properties to pulp products.Conventionally, MCF is obtained through mechanical treatment of pulpfiber by refining, followed by high pressure homogenization. Refiningproduces external fibrillation of fibers by gradually peeling off theexternal cell wall layers (P and S1 layers) and exposing the S2 layer.Internal fibrillation loosens the fiber wall. Refining is common in thepaper industry and is accomplished using a refiner. For example, in adisk refiner, a dilute fiber suspension is forced through a gap betweenthe rotor and stator disks and the fibers are subjected to repeatedcyclic mechanical stresses. The treated fibers are then homogenized bypumping the slurry of cellulose fibers through a spring-loaded valveassembly. As the valve opens and closes rapidly, the fibers aresubjected to a large pressure drop with shearing and impact forces whichpromotes a high degree of microfibrillation of the cellulose fibers,resulting in MCF. Enzymes may be used to pretreat the pulp fiber. Posttreatments may include grinding. Grinding comprises passing thehomogenized fiber solution to a grinder, made from a static grind stoneand a rotating grind stone. See for example, U.S. Pat. Nos. 6,214,163and 6,183,596.

MCF has been characterized by microscopy, such as scanning andtransmission electron microscopy and atomic force microscopy, tocomprise interconnected web-like structures of tiny fibrils andmicrofibril bundles, and diameters of the fibers range from 1 to 100 nm.A substantial part of the fibrils in MCF are relatively uniform in size.The length may by from about 100 nm to more than 1 mm. The surface areato volume of MCF is increased compared to the original pulp fibers.

In general, MCF is a form of expanded high volume cellulose in whichcellulose fibers are opened up and unraveled to expose smaller fibrilsand microfibrils. MCF comprises nanostructures that provide highstiffness and strength, crystals with self-organizing effects, andhydroxyl groups at the surface, which provide reaction sites formodification. When MCF is added to a pulp, the pulp product has improvedstrength, including the tensile strength, burst strength and tearstrength, and other characteristics such as density, smoothness and mayincrease the air permeability of the pulp product, such as an article ofthe present invention. Matrix materials of the present inventioncomprise MCF, and, similar to pulp compositions containing MCF, showincreased retention and absorption of liquids, such as dyes andolfactory-active compositions.

MCF may be added to coating materials which are used to coat pulp matrixmaterials, and may be used in an article of the present invention. MCFadded to a coating material may aid in improving the printability of thecoated surface and may aid in increasing the viscosity of the coatingmaterials to reduce streaking. MCF may also be used as a carrier forother substances, such as dyes, pigments or olfactory-active substances.

MCF properties include fine scale-high surface area, high crystallinecharacteristics, increased stiffness and strength added to pulp productscomprising MCF, and hydroxyl groups for chemical and physicalmodifications such as are known to those skilled in the art.Commercially available MCF may be used as an additive for matrixmaterials of the present invention, made for example from hardwood, pulpor from softwood. A commercial source for MCF is MCF-lyocellmicrofibrillated fiber from Engineered Fibers Technology, LLC, which hasa high number average of microfibrils with diameter of 0.1-0.25 mm MFCmay be further refined using for example, Valley Beater equipment.

When adding MCF to a pulp solution, MCF may comprise from 0.001% to 50%of the pulp composition, from 0.01% to 50%, from 0.1% to 50%, from 1.0%to 50%, from 10% to 50%, from 0.01% to 45%, from 0.01% to 40%, from0.01% to 30%, from 0.01% to 20%, from 0.01% to 10%, from 0.1% to 10%,from 1.0% to 10%, from 0.001% to 10%, from 0.01% to 1%, from 0.001% to1.0%, from 5% to 20%, and all ranges thereinbetween are included.Addition of MCF to a pulp results in a pulp matrix material, that, whencompared to a pulp matrix material without MCF, has differentcharacteristics, including but not limited to, improved tensilestrength, improved water absorption capacity-Cobb value, and improvedvapor transfer ability (MTVR).

An additive of the present invention comprises glue, an adherentmaterial. Glues are known to those skilled in the art, and choosing aglue with the desired adherent properties can be determined by thoseskilled in the art. A glue may or may not also comprise anolfactory-active substance. A glue may act as an inhibitor of release ofan olfactory-active composition, thus lengthening the time an articlereleases the olfactory-active composition. A glue may be applied in auniform or non-uniform manner to a matrix material. For example, in arod shaped structural component made from a wound paper matrix, whetherspiral wound or not, a glue may be used to adhere one or more layers ofthe paper together. Glue may be applied as dots on one or more layers orplys and the glue may serve as a spacer between the plys to create voidsbetween the layers.

An aspect of the present invention comprises adding one or moreolfactory-active substances to one or more of a pulp, to a matrixmaterial made from pulp, to the structural component made from thematrix material, or to each of a pulp, the matrix material, and thestructural component. Olfactory-active substances include but are notlimited to, fragrances, repellants, odor-eliminating compounds,aromatherapy compounds, natural oils, water-based scents, odorneutralizing compounds, and cyclodextrins. As used herein,“olfactory-active substance” refers to any compound, mixture orsuspension of compounds that are odorous, or compounds mixture orsuspension of compounds that cancel or neutralize odorous compounds,such as any compound or combination of compounds that would produce apositive or negative olfactory sense response in a living being that iscapable of responding to olfactory compounds, or that reduces oreliminates such olfactory responses. A fragrance of the presentinvention comprises an aroma or odorous compound, mixture or suspensionof compounds that is capable of producing an olfactory response in aliving being capable of responding to olfactory compounds, and may bereferred to herein as odorant, aroma, or fragrance. An olfactory-activecomposition as used herein comprises one or more olfactory-activesubstances and is generally a composition that has a smell or odor,which may be volatile, which may be transported to the olfactory systemof a human or animal, and is generally provided in a sufficiently highconcentration so that it will interact with one or more olfactoryreceptors. A fragrance composition may include one or more than one ofthe fragrance characteristics, including topnotes, midnotes or heart,and the drydown or base notes. An olfactory composition may compriseother diluents or additives, such as solvents or preservatives.

Synthetic wood materials, such as cellulosic-reinforced plasticcomposites are contemplated by the present invention. Cellulosic refersto cellulose acetates and cellulose acetate esters and includes, but isnot limited to, cellulose acetate, cellulose acetate propionate, andcellulose acetate butyrate. Cellulose acetate esters include, but arenot limited to, cellulose diacetate and cellulose triacetates. The termcellulosic also includes all hydrates of cellulosics (e.g., anhydrouscellulose acetate, cellulose acetate monohydrate, cellulose acetatedihydrate, cellulose acetate trihydrate, and cellulose acetatetetrahydrate) as well as anhydrous forms of cellulosics. Suitablepurified cellulosic pulps include Ultranier-J, Rayfloc-J-LD,Porosanier-J-HP, Ethenier-F-UHV, Sulfatate-H-J-HD and Placetate-F, eachof which are available from Rayonier, Specialty Pulp Products (Jessup,Ga. and Fernandina Beach, Fla.). These cellulosic pulps have analpha-cellulose purity of 95% or greater with the exception of Rayfloc-J(about 86% alpha-cellulose content). All are softwood pulps with theexception of Sulfatate-H-J which is manufactured.

Biomass plastics are contemplated by the present invention and arederived from renewable plant resources such as cornstarch, cellulose,and soy bean oil, rather than limited fossil resources, such aspetroleum. Renewable resources are a more viable and promisingalternative for the plastics industry. Cellulose acetate is one of themost important synthetic organic esters because it is made fromcellulose, the most abundant biopolymer on earth. Cellulose acetate isbiodegradable by certain microorganisms, and is made from renewableresources, such as wood pulp, agricultural refuse or cotton fiber.Cellulose acetate can be used as a film or as a fiber, and the fiberscan be woven into fabric which resists mildew and mold and may be formedinto matrix materials. In an embodiment of the present invention,cellulose acetate is the matrix material that is used to form a fiberbundle to make a structural component, for example, a cylinder. Thecylinder may be solid or have a hollow axis. The cellulose acetatecylinder may be treated with coatings, or may have a coating or barrier,such as a paper wrapping around the outer surface, to aid in controlledrelease of one or more olfactory-active compositions.

An exemplary embodiment of a cellulosic-reinforced plastic compositionexhibits excellent physical properties and moldability characteristics.An exemplary embodiment of a cellulosic composite material compositionis generally comprised of a plastic resin and a cellulosic fillermaterial in a range of particular proportions, and may be produced ineither a solid or a foamed form. Moreover, the ingredients of thecomposite may be made from recycled or virgin materials.

Plastic resins and cellulosic fillers may be combined. For example, anarticle of the present invention may comprise a structural componentcomprised of a matrix material of a cellulosic pulp, such as celluloseacetate and a resin, and may be formed into a suitable shape, forexample a rod, around which a paper is placed. Suitable thermoplasticresins may include: multi-layer films; high-density polyethylene (HDPE);low-density polyethylene (LDPE); polyvinyl chloride (PVC); chlorinatedpolyvinyl chloride (CPVC); semi-rigid polyvinyl chloride (S-RPVC);polypropylene (PP); ethyl-vinyl acetate; acrylonitrile butadiene styrene(ABS); polystyrene; and other similar or suitable polymers andcopolymers. Optional thermoset materials may include: polyurethanes(e.g., isocyanates); phenolic resins; epoxy resins; unsaturatedpolyester; and other similar or suitable thermoset materials. Cellulosicmaterials acceptable for use in such a composite may include: sawdust;newspapers; alfalfa; wheat pulp; wood chips; wood fibers; woodparticles; ground wood; wood flour; wood flakes; wood veneers; woodlaminates; paper; cardboard; straw; cotton; rice hulls; coconut shells;corn cobs; peanut shells; bagasse; plant fibers; bamboo fiber; palmfiber; kenaf; jute; flax; and other similar or suitable cellulosicmaterials.

Many other materials may also be added to a composite to improve itsproperties or improve processing. These materials may include inorganicfillers, cross-linking agents, blowing agents, foaming agents, foammodifiers, lubricants, stabilizers, accelerators, inhibitors, enhancers,compatibilizers, thermosetting agents, process aids, weatheringadditives, rubber, colorants, mildew inhibitors, and other similar orsuitable additives.

Methods of the present invention comprise making a pulp composition witha plastic resin, cellulosic filler material such as cellulose acetate,and other optional materials that may be caused to interact and form amatrix material composition. For example, a proper ratio of each of thecomponents may be fed via a separate hopper or similar article into amold or molding machine, e.g., an extrusion system, during the moldingoperation. Alternatively, the plastic resin and optional materials maybe pre-mixed. Separate hoppers or a similar article may then be used tointroduce the pre-mixed materials and cellulosic filler material into amold or molding machine during the molding operation. Another methodmixes the cellulosic filler with the plastic resin (plus some or all ofany optional additives, if desired) prior to introducing the mixture tothe mold or molding machine. Still another method allows for properratios of each of a thermoplastic resin, the cellulosic filler material,and the other optional materials to be fed into a compounder. Thecompounder is then used to combine and melt the individual componentsinto a pelletized feedstock, which may then be cooled and stored forlater use in a molding machine. The composition produced by thecompounder does not, however, have to be pelletized and stored. Thecomposite melt may alternatively be transported from the compounderdirectly to an extruder or other molding machine for immediate use.

Yet another method provides for the plastic resin, the cellulosic fillermaterial, and some or all of the other optional materials to be combinedin a mixer or blender. Although the blender or mixer may be heated, thecomponents may remain unmelted during mixing. The unmelted, mixedmaterial may then be stored for later use, or immediately transferred toa dryer to lower the moisture content of the cellulosic filler material.After drying, the unmelted, mixed material is preferably fed to amolding machine connected to the dryer, or may be placed in acompression mold. Other components may be added to the mixed, driedmaterial at the molding machine. Furthermore, each of the aforementionedmanufacturing methods may be varied.

Pulp compositions, such as cellulosic-reinforced plastic compositionsand other pulp compositions disclosed herein may be used to producematrix materials, structural components and articles by any of thetraditional molding means, including, but not limited to, extrusion,compression molding, and injection molding. A profile die may beutilized during extrusion to shape a pulp composition as desired. Apacker die may be used to further compress a pulp composition andimprove the bonding of the pulp composition components. Compressionmolding of a pulp matrix material composition may be achieved by placinga dry-blended or pelletized form of a pulp matrix material compositioninto a compression mold and compressing the material under sufficientheat and pressure. Regarding compression molding, it has also been foundthat a variety of secondary sheet materials may be bonded to the surfaceof a pulp matrix material composition, either during the compressionmolding process, or afterwards by using certain adhesives orcompatibilizers. Similarly, structural components or articles may alsobe produced by traditional injection molding means, utilizing molds andmolding equipment designed for the properties and characteristics of apulp matrix material composition.

An article of the present invention comprises a structural componentcomprising one or more olfactory-active compositions. A structuralcomponent may be made of pulp or any matrix material that is capable ofreleasably retaining one or more olfactory-active compositions. As usedherein, releasably retained means that a compound or composition ismaintained in or on a material, as in retained, and is capable of movingfrom one area of the material to another area of the material, or iscapable of exiting the material. All or a portion of an olfactory-activecomposition may be releasably retained by a matrix material or astructural component. For example, an olfactory-active composition maybe absorbed by the matrix material or adsorbed to a matrix material, andthe olfactory-active composition is said to reside or be present in thematrix material, and under certain conditions or as a factor of time,all or a portion of the olfactory-active may move within the matrixmaterial or exit the matrix material. A structural component mayparticipate in or control the release of all or a portion of one or moreolfactory compositions to the surrounding environment. A structuralcomponent may comprise a plastic material, such as a porous plastic thatis resistant to an olfactory-active composition. The plastic materialmay form a container in which a gel matrix material is provided and thegel matrix material may comprise an olfactory-active composition. Theolfactory-active composition may be released by diffusion from the gelmatrix material through the plastic, such as through pores in theplastic, or through an area of the plastic container in which an openingis provided.

An article of the present invention comprises a structural componentmade from a matrix material and an olfactory-active composition. Anarticle of the present invention may comprise a matrix materialcomprising an olfactory-active composition that was added directly tothe matrix material, prior to formation of the matrix material into astructural component. An article of the present invention may comprise amatrix material formed into a structural component and after formationof the structural component, an olfactory-active composition is added. Amatrix material may be a pulp composition.

An article of the present invention comprises a structural componentcomprising a matrix material comprising a spiral wound paper. The spiralwinding process allows for the paper to be the same or different foreach layer formed by winding the paper one complete revolution aroundthe axis of the structural component. For example, a structuralcomponent may comprise a rod shape, formed by winding the matrixmaterial, a paper matrix, around a vertical axis, so that a rod, havinga length longer than its diameter, is formed. Each layer formed by thecomplete revolution of the paper matrix around the axis may be referredto as a ply. For example, a 10 ply rod may have from one to tendifferent characteristics for each ply of the rod. Characteristics mayinclude those described herein for matrix material, and include, but arenot limited to, absorbance, tensile strength density, pH, porosity, andpolarity of the matrix material, and the type of paper or matrixcomposition.

An aspect of an article of the present invention comprises a matrixmaterial comprising a perforated paper matrix material, with holesformed through the paper matrix. A hole so formed may be “clean” or freeof chads, or may have the removed material, which by its removal formedthe hole, referred to herein as a chad, attached in some manner with thehole. If chads are maintained with the matrix, some or all of the chadsmay be present, and some or all of the chads may be attached to theirsource. Some or all of the chads may be free from the source point ofthe chad and may serve as spacers, for example, between plys of a spiralwound paper matrix rod. Chads may be removed from the paper matrixmaterial prior to forming a rod, for example, by a spiral windingprocess.

Perforations in a paper matrix, to form holes, may be made so that eachply of a structural component, such as a rod, has the same or differentnumbers of perforations as one or more other plys, or perforations indifferent or the same pattern as one or more plys of the structuralcomponent. Perforations comprise holes having a diameter of a desiredsize, for example, from about 50 microns to about 400 microns, fromabout 300 microns to about 1000 microns, from about 50 microns to about100 microns, from about 50 microns to about 1000 microns, from about 50microns to about 500 microns, from about 50 microns to about 300microns, from about 50 microns to about 200 microns, from about 500microns to about 1000 microns, from about 500 microns to about 600microns, from about 500 microns to about 700 microns, from about 500microns to about 800 microns, and all ranges therein between. The holesmay be of a uniform size, in that all perforations made are uniform indiameter, for example, about 300 microns, or the diameters may bearranged in particular patterns of differing diameter perforations, orthe diameters may be random.

There may be the same or differing numbers of holes per square inch of aply. For example, a ply may have from 100 to 1000 holes per square inch,which may be in a particular pattern or randomly created in the matrixmaterial. The perforations may be made in a matrix material, forexample, a paper, by processes known to those skilled in the art andinclude, but are not limited to, mechanical punch, laser created, andelectrostatic perforations. For example, with a paper matrix materialshaped in a long rectangle, two dimensional form, the perforations maybe zone punched, such as forming a pattern or random punching from thebeginning edge of the short side of the rectangle to the ending edge ofthe paper rectangle, or from one side the long side of the rectangle tothe other side for the complete paper, or in sections throughout thelength of the paper rectangle.

An article of the present invention comprise a structural component madefrom a paper matrix material, wherein the structural component is madeby spiral winding of the paper to form a rod, wherein the length of therod is larger than the diameter of the rod. For example, the rod has 20plys. The innermost 1-4 plys and the outermost 1-4 plys are lessabsorbent than the other plys of the rod. For example, the innermost andoutermost plys may be free from perforations, may be made from a lessabsorbent matrix, may be coated with a material to make the ply lessabsorbent, may have additives that reduce absorbency, and/or the papermay be treated to make it less absorbent. The plys between the innermostand outermost plys are more absorbent, which may result fromperforations, may have chads, may be made from a more absorbent matrix,may not be coated with a material, may have additives that enhanceabsorbency, and/or the paper may be treated to make it more absorbent.Each of the absorbent plys may have the same absorbency or may bedifferent from each other, or one or more plys may have the same ordifferent absorbency. For example, the between layers, for example, plys2-5 to 16-19, may have from 100 to 1000 perforations per square inch.Groups of plys may have the same absorbency. A gradient of absorbencymay be formed by the plys such that from the inner plys to the outerplys the absorbency increases, or from the inner plys to the outer plys,the absorbency decreases. The plys may be arranged as described hereinfor any particular characteristic, and are not limited to only onecharacteristic, but may be arranged according to several characteristic.Absorbency is described herein for convenience and is not to beinterpreted as limiting the invention. Those skilled in the art willunderstand that one or more characteristics may be varied or remain thesame for the plys.

Though not wishing to be bound by any particular theory, it is believedthat in a structural component wherein porosity is altered by providingthe same or differing perforations, the fragrance added to thestructural component may remain in a liquid state. The liquid state maybe found in the perforations of the matrix or in spaces made betweenplys, such as by chads or other spacers. Spacers may be made by fiberswithin a matrix or other materials that create a raised surface in areasof the matrix. As the fragrance is in a liquid form, it will wick to thesurface of the structural component and be released, and thus detectedin the outer environment.

An article may be manufactured by combining matrix material or astructural component with an olfactory-active composition by placing thematrix material or structural component in intimate contact, a period oftime, an interaction time, with an olfactory-active composition. Theolfactory-active composition may be in any physical state, such asliquid, solid, gel, or gas. For convenience, a liquid olfactory-activecomposition is described, but this is not intended to be limiting. Theinteraction time may depend on the concentration or type ofolfactory-active composition applied to the structural component, or howstrong or intense of an olfactory-active composition release desired,and/or the type of matrix material. For example, a rolled paper rodstructural component may be saturated with a liquid fragrancecomposition comprising approximately one (1) to three (3) grams of oneor more pure fragrances and the saturation time (interaction time) mayrange from less than one minute to a several hours, to several days. Amatrix material or structural component may be pre-treated prior toexposure to an olfactory-active composition. For example, a structuralcomponent may be placed in a drying oven to remove any residualmoisture. Further method steps comprise pressure treating or vacuumtreatments of the matrix material or structural component. Aftertreatment, the article may be dried, for example by rubbing or pattingdry, or other methods known for drying a surface. Drying steps may beused before or after other steps described herein.

An article of the present invention may comprise a structural componentand an olfactory-active composition comprising a fragrance compositionthat is a pure fragrance as is understood in the perfumery industry. Apure fragrance may be 40% to 50% an essential oil. A structuralcomponent may comprise a matrix material of food grade paper rolled intoa wound paper rod. For example, a 5.5 inch length wound paper rod with a15/64ths diameter, may have a void volume of from about 2 to about 5g/cm³, and approximately 0.5 to 5 grams of a fragrance composition, 0.5to 4 grams, 0.5 to 3 grams, 0.5 to 2 grams, 1.5 to 5 grams, 1.5 to 4grams, 0.5 to 3 grams, 0.5 to 2 grams, 0.5 to 1 grams, 1 to 5 grams, 2to 4 grams, 3 to 5 grams or 2 to 3 grams of a fragrance composition, maybe absorbed by the rod. For a 12 inch length wound paper rod with a15/16ths diameter, approximately 0.5 to 5 grams of a fragrancecomposition, 0.5 to 4 grams, 0.5 to 3 grams, 0.5 to 2 grams, 1 to 5grams, 2 to 5 grams, 3 to 5 grams, 3 to 4 grams, 4 to 5 grams of afragrance composition, may be absorbed by the rod. The amount offragrance absorbed may depend on the matrix material, the length of timeof exposure of the fragrance composition to the matrix material, thedensity of the fragrance, the solvents of the fragrance, the porosity ofthe matrix material, the method of forming the matrix material into astructural component, and additives, coatings or treatments made to thematrix material, the structural component or the article. Suchparameters may be determined by those skilled in the art.

In the present invention, a fragrance composition is provided to amatrix material to provide a load of fragrance of at least 70%, at least75%, at least 80%, at least 85%, or at least 90%, load by weight offragrance to matrix material weight. The present invention comprisesfragrance article having at least 70% load factor of fragrancecompounds. It is known that the load of scented candles is 5-7%, airfresheners such as paper shaped like little trees have a load factor of40%, and gel fragrance article are 80-85%. For example, an articlecomprising a structural component of a rod of rolled paper matrixmaterial may have a load of 85%. For example, a 5.5 inch rolled paperrod may have 1.6 g of a pure fragrance composition per rod, using amethod of manufacture disclosed herein.

When using a matrix material of the present invention having a fragranceload factor of at least 70%, under testing and controlled conditions,the fragrance is released from the article for more than about 10 days.A rolled paper rod may show a rapid, continuous release of fragrance forthe first ten days, and as fragrance is transmitted from underlyinglayers to the outer layer, the fragrance is released at slower rateuntil the fragrance is no longer detectable. For example, an article ofthe present invention may release at least about 30% by weight of thefragrance compound/composition within the first 30 days of exposure tothe ambient air. Alternatively, an article may release a portion of thefragrance in a short amount of time, and thereafter release fragrance ina steady state.

An article of the present invention may comprise luminescent compounds.Such compounds may be added directly to a matrix material or may be inan interior compartment, inside in a plastic structure that surrounds aportion of a structural component, or as a coating on a portion of astructural component. For example, a luminol gel may be placed within acore of a rod-shaped structural component. The luminol(3-aminophthalhydrazide or 5-amino-2,3-dihydro-1,4-phthalazinedione) isactivated by addition of a mild oxidizing agent, for example, by bendingan article containing luminol slightly to break a capsule containing amild oxidizing agent, such as 0.3% hydrogen peroxide. The article thenemits the cool light provided by the chemiluminescence of luminol alongwith one or more olfactory substances.

An aspect of the invention comprises providing an article as describedherein which further comprises flavor compounds, which may beincorporated into or replace one or more olfactory-active compositions.Flavor compounds may be provided in compositions comprising solvents ordiluents or other additives.

A structural component may be formed into any shape desired for aparticular application. Once the matrix material is formed or made intothe structural component, the structural component may be formed into adesired shape. For example, the structural component may be formed intotwo dimensional shapes such as sheets, disks, circles, triangles,polygons, rectangles, or patterned formats. The two-dimensional shapesmay have differing sizes. The structural component may be formed intothree dimensional shapes have differing sizes. The three-dimensionalshapes may be solid or may comprise a compartment. The three-dimensionalshapes may be hollow. For example, suitable three-dimensional shapesincludes, but are not limited to, solid or hollow axis rods havingvarious sorts of circumferences like circular, hexagonal, pentagonal,triangular, etc., balls, pellets, and other desired likeness. Forexample, an aspect of the present invention comprises rod-shapedstructural components formed from a matrix material of paper that iswound around a central axis to form a tightly wound paper rod. A rod maybe of any desired length and/or shape depending upon the application.

The structural component may be formed by any of the traditional moldingmeans, including, but not limited to, extrusion, compression molding,and injection molding of the matrix material, for example, a pulpcomposition. A profile die may be utilized during extrusion to shape thematrix material as desired. A packer die may be used to further compressthe matrix material and improve the bonding of the individual materialcomponents. Compression molding of the matrix material may be achievedby placing a dry-blended or pelletized form of the composition into acompression mold and compressing the matrix material under sufficientheat and pressure. Regarding compression molding, it has also been foundthat a variety of secondary sheet materials may be bonded to the surfaceof the matrix material, either during the compression molding process,or afterwards by using certain adhesives or compatibilizers. Similarly,articles may also be produced by traditional injection molding means,utilizing molds and molding equipment designed for the properties.

A structural component or a matrix material may be made using anelectrospinning process. Electrospinning uses an electric field to drawa solution from the tip of a capillary to a collector. A voltage isapplied to the solution, which causes a jet of the solution to be drawntoward a grounded collector. The fine jets dry to form fibers, which canbe collected, for example, on a web.

An aspect of the present invention comprises a rod-shaped structuralcomponent wherein the interior of the rod is hollow. For example, in awound paper rod, the wound paper forms an open area throughout the axisof the wound paper rod. The matrix material forms a walled structureencompassing a compartment through the longitudinal length of the rod.Alternatively, a pulp composition, matrix material, may be formed into ahollow rod in which the central axis encompasses a compartment throughthe longitudinal length of the article. The compartment, referred to asan interior compartment, is open to the exterior of the rod at each endof the rod. Also contemplated in the present invention are rods, made byany method known, which do not have a hollow central axis.

The interior compartment may comprise an olfactory-active composition,an olfactory-active composition gel, or other compositions. For example,the interior compartment may be filled with compounds that create anexothermic reaction. The exothermic reaction heats an olfactory-activecomposition in the matrix material and enhances the release rate of theolfactory-active composition. Exothermic reactions are known to thoseskilled in the art. For example, calcium oxide (quicklime) reacts withwater to release heat. A small container of water is provided within theinterior compartment of the matrix material. A user can pierce the watercontainer, or break it open by bending the rod slightly, releasing thewater to react with the calcium oxide. A similar reaction may be madewith copper sulfate and zinc, anhydrous calcium chloride and water, acidand base neutralization reactions, such as sodium bicarbonate and anyweak acid, for example acetic acid, and oxidation or polymerizationreactions that yield heat. The open ends of the interior compartment maybe capped, crimped or closed, or sealed in any manner, so as to retainthe materials within the interior compartment.

Exothermic reactions may be provided by the reaction of a compound in anolfactory-active composition that reacts with another compoundincorporated throughout the matrix material. For example, sodiumbicarbonate particles are incorporated into the matrix material, forexample sprinkled onto paper as it is rolled into a paper rod andcreating an interior compartment. The olfactory-active composition isadded to the rolled paper rod by inserting the olfactory-activecomposition into the interior compartment. As the olfactory-activecomposition passes from the interior compartment into and through therolled paper matrix, a reactant in the olfactory-active composition,such as an acid, reacts with the sodium bicarbonate and produces heat.The heat produced changes the movement of the olfactory-activecomposition and its release into the environment.

An interior compartment may contain an olfactory-active composition,such as a fragrance, that is in a liquid or gel state and fills at leasta portion of the interior compartment. The olfactory-active compositionmay exit the compartment through the walls forming the interiorcompartment and/or may exit through the material sealing the formerlyopen ends of the interior compartment.

A structural component may be made with a honeycomb design asexemplified in FIG. 1. One or more of the interior chambers formed bythe honeycomb may be filled with materials such as gels, fragrancecompounds, olfactory-active compositions or other materials, or may beempty or hollow. The honeycomb structure may be made of one material ormay be made of more than one material, and may or may not be coated.

A structural component may be made with a multi-core design as shown inFIG. 2. For example, a core of material forms the central axis of a rodshaped structural component. Another type of material surrounds the corematerial, as is shown in FIG. 2. Aspects of the invention comprisemulti-core structural components, wherein one or more types of material,in different layers, surround the core material. The core material maybe made from a single matrix composition, such as a pulp and nanofibercomposition, or may be made from a combination of matrix compositions.One or more of the cores (or layers of the structural component) maycomprise an olfactory-active substance, which may be the same ordifferent in different cores or layers. Having different layers or coresof a structural component may aid in control release of one or moreolfactory-active substances. Additives may be provided in thecompositions forming the one or more layers or cores of a structuralcomponent.

An article of the present invention may comprise a structural componentcomprising a core made of a matrix material that is different from thematrix surrounding the core. For example, the structural component maycomprise a core that is a sponge and the surrounding material may bemade of a paper or pulp matrix described herein. Thus the article has adual matrix material structural component. For example, the structuralcomponent may have a rod shape, with the axis of the rod formed by acore comprising a sponge matrix, and the surrounding material comprisinga paper matrix applied by a spiral winding process around the core. Theolfactory-active composition may be the same or different in the coreand the surrounding material. The core matrix material may form themajority of the rod with a smaller amount of the surrounding materialforming an outer shell around the core. For example, the core may be aliquid, gel, sponge, pulp matrix or any matrix that serves as anolfactory-active composition reservoir, and the surrounding material mayserve a control release function for the olfactory-active composition.For example, the outer surrounding matrix material may be a spiral woundpaper having plys with the same or different absorbency, or othercharacteristics, that may allow for the controlled release of theolfactory-active composition from the core.

A matrix material is the material that makes up the structural componentof an article. An example of a matrix material is a pulp composition,which may or may not comprise additives. The matrix material may havevarying characteristics including, but not limited to, base sheetphysical properties, mechanical properties, bulk properties, color, andspecial features. Basis weight, thickness, width, and length areimportant physical properties to consider. Mechanical properties includeboth tensile strength and tear strength. Dielectric strength, electricalresistivity, thermal conductivity, and maximum use temperature areexamples of bulk properties. The color may be determined by the positionin a three-dimensional coordinate system in which one axis is thepaper's brightness from 0 to 100%, another axis is the green/reddirection, and the third axis is the blue/yellow direction. Brightness,opacity, and clarity are characteristics. Articles may be designed toresist flame, smoke, chemicals, ultraviolet (UV) light, or behydrophilic, hydrophobic, recyclable, or tamper-evident. A paper usablein an article of the present invention comprises a low acid or acid freepaper. Acid-free paper is paper that has a neutral or basic pH (7 orslightly greater). It can be made from any cellulose fiber as long asthe active acid pulp is eliminated during processing. It may also belignin- and sulfur-free. A paper that may be used in an article of thepresent invention comprising a rolled paper rod comprises an uncoatedfree sheet, a basis weight #24, with a 17″ by 22″ basis, as is known inthe paper industry. Bond paper may be used that has an alkaline pH.

Examples of matrix material contemplated by the present inventioninclude paper, laminated papers, rolled paper, compressed paper,plastics, cellulose acetate, cellulose materials such as methycelluloseor carboxymethylcellulose formed into a shape, cardboard, particleboard, pressed wood, wood, fabric, woven or nonwoven fabrics, fibersfrom natural or synthetic sources, bamboo, recycled materials, manilahemp, carboxymethylcellulose, cellulose gums, hydrolyzed acrylonitrilegraft copolymer, neutralized starch-acrylic acid graft copolymer,acrylamide copolymer, modified crosslinked polyvinyl alcohol,neutralized self-crosslinking polyacrylic acid, crosslinked polyacrylatesalts, neutralized crosslinked isobutylene-maleic anhydride copolymers,or salts or mixtures thereof.

A matrix material may be made of fibers and other compounds orcompositions. For example, a matrix material may comprise paper fibersand absorbent compounds. For example, a matrix material comprising25-30% calcium carbonate may have improved absorbency capabilities. Thepresent invention comprises an article made with a matrix material thatis substantially free of calcium carbonate. For example, the matrixmaterial may have less than 10% calcium carbonate, less than 5% calciumcarbonate, less than 1% calcium carbonate, less than 0.10% calciumcarbonate, less than 0.010% calcium carbonate, to substantially 0%calcium carbonate.

An example of a matrix material comprises a functional wicking materialcomprising a binder fiber adhered to a hydrophilic functional fiber,wherein the binder fiber is a staple bicomponent or monocomponent fiberoriented in substantially the same direction as the hydrophilic fiber.Examples of monocomponent binder fibers include, but are not limited to,PE, PP, PS, nylon-6, nylon-6,6, nylon-12, copolyamides, PET, PBT, andCoPET. Preferred bicomponent binder fibers made of polyethylene/PET,polypropylene/PET, or CoPET/PET. Monocomponent binder fibers are PE, PP,or PET. Examples of suitable hydrophilic functional fibers include, butare not limited to, high absorbent rayon, Lyocel or Tencel, hydrophilicnylon, hydrophilic acrylic fibers, and cellulosic based high absorbentfibers. A functional wicking matrix material comprises from about 1 toabout 98 weight percent, from about 5 to about 95 weight percent, orfrom about 5 to about 50 weight percent of binder fiber. A wickingmatrix material comprises from about 5 to about 70, from about 5 toabout 55, or from about 10 to about 40 weight percent of functionalfiber. For examples, see U.S. Patent Publication 20030211799.

A structural component may comprise a rolled paper rod wherein thematrix material paper is perforated at regular intervals to formattached “sheets” of paper, so that a sheet is substantially one layerof the multi-layer rolled rod. One can remove a layer from the surfaceof the rod by removing one sheet of the paper. As a layer is removed,the underlying sheet is exposed to the exterior and can provide asurface area for releasing an olfactory-active composition to theenvironment.

A matrix material may be an extruded plastic material which absorbs theolfactory-active composition. A matrix material may comprise a fibrousmaterial comprised of a binder fiber adhered to a functional fiber,wherein the binder fiber is a staple bicomponent fiber oriented insubstantially the same direction as the functional fiber. The functionalfiber can be a staple or continuous fiber. Examples of suitable binderfibers include, but are not limited to, bicomponent fibers made of thefollowing pairs of polymers: polypropylene/polyethylene terephthalate(PET); polyethylene/PET; polypropylene/Nylon-6; Nylon-6/PET;copolyester/PET; copolyester/Nylon-6; copolyester/Nylon-6,6;poly-4-methyl-1-pentene/PET; poly-4-methyl-1-pentene/Nylon-6;poly-4-methyl-1-pentene/Nylon-6,6; PET/polyethylene naphthalate (PEN);Nylon-6,6/poly-1,4-cyclohexanedimethyl-1 (PCT);polypropylene/polybutylene terephthalate (PBT); Nylon-6/co-polyamide;polylactic acid/polystyrene; polyurethane/acetal; and solublecopolyester/polyethylene. Examples of functional fibers include, but arenot limited to, nylons, cellulose-based materials, polyvinyl alcohols(e.g., phosphorylated polyvinyl alcohol), superabsorbent fibers, carbonfibers, glass fibers, ceramic fibers, and acrylic fibers. Fibrousmaterials may have a density of from about 0.15 g/cm³ to about 0.8g/cm³, from about 0.2 g/cm³ to about 0.65 g/cm³, and from about 0.25g/cm³ to about 0.5 g/cm³.

The matrix material may be selected so as to provide controlled releaseof all or a portion of an olfactory-active composition, or to aid incontrol of the release of an olfactory-active composition. For example,a paper matrix may be provided that has a desired porosity. Higherporosity generally allows for faster release of an olfactory-activecomposition, and lower porosity generally allows for slower release.Additionally, the matrix material may comprise fibers having differingabsorbance rates, which may affect the release rate of anolfactory-active composition. A matrix may be made from one or moredifferently absorbing or releasing fibers and such differing fibers mayor may not provide for differing release rates of an olfactory-activecomposition. For example, a matrix made from 50% bamboo fiber and 50%paper fiber would release an olfactory-active composition at a ratedifferent from that of a matrix made from 100% bamboo fibers or 100%paper pulp fibers. For example, the matrix may comprise a sponge orsponge-like element.

A matrix material may comprise a gel material. A gel matrix material maybe of sufficient physical integrity as to hold its shape continuously.For example, a gel matrix material, comprising an olfactory-activecomposition, may be formed into a shape, such as a rod, and maintain therod shape throughout its existence. Alternatively, a gel matrix materialmay be surrounded by another material that provides the structural shapeto form the structural component of an article of the present invention.For example, a gel comprising an olfactory-active composition, such as afragrance composition, may be surrounded by a plastic sheath thatmaintains the gel in a particular shape. A portion of the plastic sheathmay be removed to allow for release of the olfactory-active compositionfrom the gel and the article. A gel matrix material may be rolled toform a structure, for example, a rod-shaped structure, and the gel maycomprise an olfactory-active composition. Gel matrix materialcompositions are known in the art and one of skill can combine a gelwith an olfactory-active composition.

Optionally, aroma-releasing polymeric gel matrices may contain one ormore additional materials that control evaporation and/or firmness ofthe polymeric gel matrix—Evaporation and/or Firmness Controlling Agent(EFCAs). Useful EFCAs include, but are not limited to, the followingesters: acetates, adipates, azeleates, benzoates, caprylamides,capramides, caprates, citrates, cocoates, fumarates, glutarates,glycolates, heptanoates, isobutyrates, isophthalates, laurates,linoleates, maleates, mellitates, myristates (e.g., isopropylmyristate), octanoates, oleates, palmitates (e.g., isopropyl palmitate),pelargonates, phosphates, phthalates, ricinoleates, sebacates,stearates, succinates, toluates, toluamides, tallates, benzyl benzoate,di-2-ethylhexyl phthalate, proprietary blend of esters and phthalates,diethyl phthalate, dioctyl terephthalate, dioctyl adipate, hexanedioicacid polymer with 1,4-butanediol and 1,2-propanediol didecanoate,benzyl3-isobutyryloxy-1-isopropyl-2,2-dimethyl-propyl phthalate, anddecanoates. Other suitable EFCAs include diproplylene glycol, hexyleneglycol, isoparafinic hydrocarbons, including those sold under thetradename Isopar M by ExxonMobil (Houston, Tex.), polymeric PVCplasticizers, including those sold under the Tradename Admex by VelsicolChemical Corp. (Rosemont, Ill.), and odorless mineral spirits.

A matrix material may comprise absorbent compositions. For example, amatrix material may comprise chalk, which is composed mostly of calciumcarbonate with minor amounts of silt and clay, or the mineral gypsum(calcium sulfate). Such a chalk composition may be formed into a rodmade of compressed powder, of any desired length. The structuralcomponent of chalk matrix material may be treated as described hereinfor other materials or structural components such as coated, coloredand/or sheathed.

An aspect of the present invention comprises an article made with matrixmaterials that are stable, in that the matrix does not readilydecompose, fall apart, unravel, shred, fracture, break or tear. Onceformed, the matrix material is sufficiently sturdy to remainsubstantially intact when exposed to the environment or its intendeduse. An aspect of a matrix material is that the material is not brittleor friable to the touch and handling the matrix material in a typicaluse or manner does not cause breakage or pieces to dislodge. An aspectof the present invention comprises an article made with biodegradablematrix materials. An aspect of the present invention comprises anarticle made with recycled materials, or may be recyclable. Suchmaterials may be fully or partially made with recycled material.

A treatment of the matrix material may occur or be applied before, orafter, an olfactory-active composition is added to the matrix material.One or more treatments may be used with a particular matrix, and anolfactory-active composition may be added to the matrix before or afterany one or all of the treatments to the matrix. One or more treatmentsmay be controlled release elements of the article. One or moretreatments may increase or decrease the rate of release of the fragrancefrom the article.

A coating applied to a matrix material or to a structural component mayfunction as a barrier and thus retard release of an olfactory-activecompound from the matrix material or structural component. As usedherein, a coating, applying a coating and a coating composition refer toproviding this bather function to a matrix material or a structuralcomponent. Coating of a matrix material may occur before the matrixmaterial is formed into the structural component of an article or mayoccur after the structural component is formed. For example, a paper maybe coated with a wax while the paper is in a sheet or roll form, and thecoating may be over all or a portion of the paper. The wax coating maybe over an area of the paper, for example the wax coating covers an areaan inch from one margin, or the coating may cover the paper from marginto margin but only be applied on the paper roll every other meter, sothat some of the roll is coated and some is not. A coating applied to amatrix material may be in a pattern, such as a grid, applied to coverone entire surface, or may be randomly applied.

Coating compositions may comprises waxes, including but not limited tosoy waxes, paraffins, and bees waxes. The wax may be coated onto amatrix material or a structural component using a flood coating method,wherein a wax is diluted in a solvent, such as a volatile solvent, andall outer surfaces are uniformly coated, for example, with a 1-10 micronlayer of wax. A wax may be diluted in pentane. The coating may coatouter surfaces, including an outer surface that forms the inner surfacethat would be next to a core material. For example, in a rod shapedarticle shaped like a drinking straw, both the outer surface and theinner bore surface may be coated with a material, such as a wax. Waxescontemplated by the present invention comprise waxes known to thoseskilled in the art. A hydrophobic or hydrophilic solvent may be used ina coating composition.

Microcrystalline waxes differ from refined paraffin wax in that thecrystal structure is more branched and the carbon chains are longer.These waxes are tougher, more flexible and have higher tensile strengthsand melting points. They are also more adhesive, and they bind solvents,oil, etc., and thus prevent the sweating-out of compositions.Polyethylene waxes are manufactured from low molecular weight,high-density raw materials, designed to give the particular performancecharacteristics required by industry.

Waxes that may be used as coating compositions comprises waxes thatsoften or melt at a temperature about 150 F, or in excess of 200 F. Forexample, the High-Melt Straight Paraffin product from InternationalGroup Inc, IGI 1260-SLAB has a melting point of 163 F. Synthetichydrocarbon waxes may have high melting points—e.g. 210 F.

Coating compositions may comprise acrylates. For example, coatingcompositions may be made with polyester polymers, such as polylactide,polyglycolide or polycaprolactone, or a polyester copolymer selectedfrom poly(lactide/glycolide) acid (PLGA) orpoly(lactid-co-.epsilon.-caprolact-one) (PLCL), alkyl- oralkoxyalkyl-2-cyanoacrylates such as n-butyl-2-cyanoacrylate or2-methoxybutyl-2-cyanoacrylate, crosslinked cyanoacrylate, polylacticacid, polyglycolic acid, lactic-glycolic acid copolymers,polycaprolactone, lactic acid-caprolactone copolymers,poly-3-hydroxybutyric acid, polyorthoesters, polyalkyl acrylates,copolymers of alkylacrylate and vinyl acetate, polyalkyl methacrylates,and copolymers of alkyl methacrylates and butadiene; and plasticizerssuch as dioctyl phthalate, dimethyl sebacate, trethyl phosphate,tri(2-ethylhexy)phosphate, tri(p-cresyl)phosphate, glyceryl triacetate,glyceryl tributyrate, diethyl sebacate, dioctyl adipate, isopropylmyristate, butyl stearate, lauric acid, dibutyl phthalate, trioctyltrimellitate, and dioctyl glutarate.

Coating compositions may include polymers or copolymers containing, forexample, caprolactone, poly-.beta.-hydroxybutyrate, delta-valerolactone,as well as polyvinylpyrrolidone, polyamides, gelatin, albumin, proteins,collagen, poly (orthoesters), poly(anhydrides), poly(.alpha.-cyanoacrylates), poly (dihydropyrans), poly(acetals),poly(phosphazenes), poly(urethanes), poly(dioxinones), cellulose,proteins and starches. A coating contemplated by the present inventioncomprises Krylon® Triple-Thick crystal clear glaze, commerciallyavailable from Krylon Products Group, Cleveland, Ohio.

The matrix material may also be coated after the matrix material isformed into the structural component of an article. For example, if astructural component is a rod, a coating may be applied to one or bothof the ends of the rod. A coating may be applied to all or a portion ofa structural component, such as on one side. A coating may be applieduniformly to a structural component or may be applied in a pattern orrandom application, such as spraying or sputtering.

The coating may function as a control release element of an article. Apattern coating may act as a screen door so as to impede some materialsand allow others to pass. A pattern coating may be in a grid, instripes, in any determined pattern or in no particular pattern, such asrandomly applied. For example, adding a wax or plastic coating to astructural component may impede the release of an olfactory-activecomposition from an article. The coating may or may not degrade withtime. For example, if the coating impedes the release of anolfactory-active composition, with time, as the coating degrades, thereis more surface area for release of fragrance and less impedance of anolfactory-active composition release. Another example of coatingprovides for shielding or directing an olfactory-active composition in aparticular direction. A structural component may be coated in aparticular area and prevent release of an olfactory-active compositionin that area. For example, if an article, comprising a fragranceolfactory-active composition, is placed with delicate foliage, the sideof the article facing the foliage can be coated to prevent fragrancerelease toward the foliage and avoid any effects on the foliage.

A coating may function as a control release element for the release ofan olfactory-active composition from an article of the presentinvention. A coating may allow an article to provide a particular levelof an olfactory-active composition from the article for a determinedtime period. A coating may allow for a precise control release rate. Forexample, a coating on a matrix material may inhibit release of anolfactory-active composition so that an olfactory-active composition isreleased over a longer time period than is an uncoated matrix material.

Matrix material may undergo other treatments, which may be optional,such as dying of the matrix material. Dyes include natural and syntheticdyes, water-resistant dyes, oil-resistant dyes, and combinations ofwater- and oil-resistant dyes. Dyes may be selected based on thecomposition of the matrix material, and is well within the skill ofthose in the art. Suitable water-resistant dyes include oil soluble dyesand wax soluble dyes. Examples of oil soluble dyes include PylakromeDark Green and Pylakrome Red (Pylam Products Company, Tempe Ariz.).Suitable oil-resistant dyes include water soluble dyes. Examples ofwater soluble dyes include FD&C Blue No. 1 and Carmine (Sensient, St.Louis, Mo.). A Lake type dye may also be used. Examples of Lake dyes areCartasol Blue KRL-NA LIQ and Cartasol Yellow KGL LIQ (ClariantCorporation, Charlotte, N.C.). Pigments may also be used in coloring thematrix materials and may be added during or after the manufacture of thematrix material. Such coloring or dying methods are known to thoseskilled in the art, and any suitable dyes, pigments or colorants arecontemplated by the present invention.

Paper or other matrix materials may be treated or undergo secondaryprocessing before use in an article of the present invention. Forexample, there are many secondary processes, examples include sizing,calendering, glazing, saturation, coating, folding, corrugating,perforating, slitting, and sheeting. Sizing is the process of lightlycoating one or both surfaces of a paper with a starch solution toenhance surface properties. Calendering presses paper between two rollsunder high pressure. As paper density and surface smoothness increase,porosity and thickness decrease. Glazing produces similar results, butuses a moving ball to apply high pressure to only one side of the paper.Saturation is an immersion process in which paper is fullywetted—typically with a latex dispersion—and subsequently dried. Coatingapplies one or more layers of material to one or both surfaces of apaper. For example, paper may be coated with wax. A coating may beapplied as a liquid that then solidifies on a matrix material, or acoating may be a tape or sleeve that is applied to the matrix materialor over all or a portion of the matrix material. For example, a matrixmaterial may be dipped into a coating, sprayed with a coating, or acoating may be a tape that is wrapped around all or a portion of thematrix material. In another aspect, where the matrix material is formedinto a rod, a sleeve of fluid impervious plastic is slipped over one endof the rod to cover the bottom and lower edge of the rod. A matrixmaterial may be perforated in one or more sites. For example, a paper tobe used in a rolled paper rod article may have multiple pinprick holesmade in the paper prior to rolling. Such pinprick holes may formcapillaries within the rolled rod and control movement and release of anolfactory-active composition. Such perforations may be added to thematrix material after formation into the structural component.

Matrix materials may be dyed for many reasons, such as so that anarticle will blend in with the environment it is used in, to mask thecolor of an olfactory-active composition, or so that the article may benoticed because of its appearance. A matrix material or a structuralcomponent may be dyed or colored with one or more colors or hues, or mayhave a dappled or patterned appearance. Colors or dyes may be applied toa matrix material or to a coating that is then applied to a matrixmaterial. A water-resistant dye may be dissolved in a hydrophobicsolvent. Suitable hydrophobic solvents include Isopar M, petroleumdistillates, mineral oil, short or long chain alcohols, fragrances,fragrance raw materials, essential oils and other hydrophobic liquidsthat will solubilize the dye. An oil-resistant dye may be solubilizedusing a hydrophilic solvent. Suitable hydrophilic solvents includewater, short chain alcohols, short chain carboxylic acids and glycols. Acombination oil- and water-resistant dye can be solubilized in a solventinto which it will dissolve. Suitable materials include short chainalcohols. In a method of making an article of the present invention,methanol is used to dissolve and solubilize a Lake dye.

Methods of making articles of the present invention comprise applying orproviding one or more olfactory active compositions or compounds to amatrix material or a structural component. For example, a method ofmaking an scented article of the present invention comprises admixing ina container an olfactory-active composition and a structural component,such as a rod made by winding a continuous sheet of porous and/orabsorbent paper around a central axis. The continuous sheet of paper isthe matrix material. Alternatively, the matrix material may be scentedprior to forming the structural component, the wound paper rod. Where amatrix material undergoes these steps of incorporating one or moreolfactory-active compositions into the absorbent matrix material, toform a scented matrix material, the steps of forming a structuralcomponent from the matrix material follows so as to form a scentedarticle of the present invention.

A method of making a scented article of the present invention comprisesproviding an olfactory-active composition that may be applied to thematrix material or structural component. For brevity, methods aredescribed where the matrix material is contacted by the olfactory-activecomposition, though this is not to be limiting of the invention. Anolfactory-active composition may be applied to the matrix material bydipping, spraying, sputtering, absorbing, adsorbing or immersing amatrix material with an olfactory-active composition, or other methodsknown for applying a liquid, solid, gaseous or gel composition to asolid support.

A method for making a scented article comprises combining anolfactory-active composition and a matrix material or structuralcomponent in a container and applying a pressure above atmosphericpressure on the composition and the matrix material or structuralcomponent. For example, a fragrance composition and a structuralcomponent such as rolled paper rod were combined in a container in apressure treating apparatus (a sealed container) and pressure wasapplied in a range from about 1 psi to about 40 psi, from about 5 psi toabout 30 psi, or from about 10 psi to about 20 psi, at about 5 psi, atabout 10 psi, at about 15 psi, at about 20 psi, at about 25 psi, atabout 30 psi, at about 35 psi, at about 40 psi, and pressuresthereinbetween. The pressure may be applied for a period of time fromabout 10 minutes to about 10 hours, for about 30 minutes, for about 1hour, for about 2 hours, for about 3 hours, for about 4 hours, for about5 hours for about 6 hours, for about 7 hours, for about 8 hours, forabout 9 hours, for about 10 hours, or longer if needed to applysufficient amounts of olfactory-active compositions to a matrix materialor structural component to achieve a desired load of theolfactory-active composition(s) to the matrix material or structuralcomponent or release of the olfactory-active composition from the matrixmaterial or structural component.

A method for making a scented article comprises combining anolfactory-active composition and a matrix material or structuralcomponent in a container and applying a vacuum below atmosphericpressure on the composition and the matrix material or structuralcomponent. For example, a fragrance composition and a structuralcomponent such as rolled paper rod were combined in a container invacuum apparatus and a vacuum was applied in a range from about 0.001 mmHg to about 700 mm Hg, or from about 5 Kpa to about 35 kPa, from about10 Kpa to about 25 kPa, from about 20 Kpa to about 30 kPa, from about 15Kpa to about 25 kPa, from about 25 Kpa to about 30 kPa, at about 5 kPa,at about 6 kPa, at about 7 kPa, at about 8 kPa, at about 9 kPa, at about10 kPa, at about 15 kPa, at about 16 kPa, at about 17 kPa, at about 18kPa, at about 19 kPa, at about 20 kPa, at about 22 kPa, at about 24 kPa,at about 26 kPa, at about 28 kPa, at about 30 kPa, and vacuumsthereinbetween. The vacuum may be applied for a period of time fromabout 10 minutes to about 10 hours, for about 30 minutes, for about 1hour, for about 2 hours, for about 3 hours, for about 4 hours, for about5 hours for about 6 hours, for about 7 hours, for about 8 hours, forabout 9 hours, for about 10 hours, or longer if needed to applysufficient amounts of olfactory-active compositions to a matrix materialor structural component to achieve a desired load of theolfactory-active composition(s) to the matrix material or structuralcomponent or release of the olfactory-active composition from the matrixmaterial or structural component.

A method of making a scented article of the present invention maycomprise pressure and vacuum steps. An olfactory-active composition anda matrix material may be combined and undergo vacuum treatment andpressure treatment, in no particular order. For example, anolfactory-active composition and a matrix material were combined in acontainer in an air-tight apparatus and a vacuum of 20 mm Hg to 80 mm Hgwas applied for about 1 minute to 10 hours. Pressure treatment of 1 psito 40 psi may be applied for about 10 minutes to about 10 hours and thetime and amount of vacuum or pressure treatment may vary and depend uponthe amount of olfactory-active composition to be loaded in the matrixmaterial or structural component, the type of matrix material used, theintended use of the article, and other characteristics of scentedarticles.

A method for making a scented article comprises adding anolfactory-active composition to a matrix material, comprising placingone or more matrix materials or one or more structural components in aclosed container under a vacuum, such as about 0.1 to 700 mm Hg,maintaining the vacuum for 1 minute to 1 hour, for about 10 minutes, forabout 15 minutes, for about 30 minutes, for about 45 minutes,introducing at least one olfactory-active composition in an amountsufficient to cover a portion of the one or more matrix materials or oneor more structural components, optionally while maintaining the vacuum,then pressurizing the closed container containing the one or more matrixmaterials or one or more structural components and the at least oneolfactory-active composition to 10-40 psi, or 500 to 2000 mmHg for aperiod of time. The period of time may be from 1 minute to 10 hours, for15 minutes, for 30 minutes, for 1 hour, for 2 hours, for 3 hours, for 4hours, for 5 hours, for 6 hours, for 7 hours, for 8 hours, for 9 hours,for 10 hours, or longer if desired for providing an adequate load ofolfactory-active composition to a matrix material. Release of thepressure and removal of the matrix material or structural componentcomprising the absorbed olfactory-active composition follows.

A method for making a scented article, comprises, a) applying a vacuumin a closed container containing at least one structural component; b)adding a sufficient amount of a liquid olfactory-active composition tothe closed container; c) maintaining the vacuum; d) releasing the vacuumand pressurizing the closed container so that a pressure is maintainedfor a time sufficient for a portion of the olfactory-active compositionto be retained by the structural component. A method for making ascented article comprises a) applying a vacuum in a closed containercontaining at least one structural component; b) adding a sufficientamount of a liquid olfactory-active composition to the closed containerto cover the desired portion of the at least one structural component;c) maintaining the vacuum for a desired time period; d) releasing thevacuum and removing the liquid; and optionally, e) applying a vacuum tothe container comprising the at least one structural component.

Olfactory-active compounds useful in the present invention include butare not limited to, esters, terpenes, cyclic terpenes, phenolics whichare also referred to as aromatics, amines and alcohols. For example,furaneol 1-hexanol, cis-3-Hexen-1-ol, menthol, acetaldehyde, hexanal,cis-3-hexenal, furfural, fructone, hexyl acetate, ethylmethylphenylglycidate, dihydrojasmone, wine lactone, oct-1-en-3-one,2-Acetyl-1-pyrroline, 6-acetyl-2,3,4,5-tetrahydropyridine,gamma-decalactone, gamma-nonalactone, delta-octalactone, jasmine,massoia lactone, sotolon ethanethiol, grapefruit mercaptan,methanethiol, 2-methyl-2-propanethiol, methylphosphine,dimethylphosphine, methyl formate, nerolin tetrahydrothiophene,2,4,6-trichloroanisole, substituted pyrazines, methyl acetate, methylbutyrate, methyl butanoate, ethyl acetate, ethyl butyrate, ethylbutanoate, isoamyl acetate, pentyl butyrate, pentyl butanoate, pentylpentanoate, isoamyl acetate, octyl acetate, myrcene, geraniol, nerol,citral, lemonal, geranial, neral, citronellal, citronellol, linalool,nerolidol, limonene, camphor, terpineol, alpha-ionone, terpineol,thujone, benzaldehyde, eugenol, cinnamaldehyde, ethyl maltol, vanillin,anisole, anethole, estragole, thymoltrimethylamine, putrescine,diaminobutane, cadaverine, pyridine, indole and skatole. Most of theseare organic compounds and are readily soluble in organic solvents, suchas alcohols or oils. Fragrance includes pure fragrances such as thoseincluding essential oils and are known to those skilled in the art.Water-based odorous compounds and other odorus compositions are alsocontemplated by the present invention.

Fragrance oils as olfactory-active compounds or compositions usuallycomprise many different perfume raw materials. Each perfume raw materialused differs from another by several important properties includingindividual character, and volatility. By bearing in mind these differentproperties, and others, the perfume raw material can be blended todevelop a fragrance oil with an overall specific character profile. Todate, characters are designed to alter and develop with time as thedifferent perfume raw materials evaporate from the substrate and aredetected by the user. For example perfume raw materials which have ahigh volatility and low substantivity are commonly used to give aninitial burst of characters such as light, fresh, fruity, citrus, greenor delicate floral to the fragrance oil which are detected soon afterapplication. Such materials are commonly referred to in the field offragrances as “top notes”. By way of a contrast, the less volatile, andmore substantive, perfume raw materials are typically used to givecharacters such as musk, sweet, balsamic, spicy, woody or heavy floralto the fragrance oil which, although may also be detected soon afterapplication, also last far longer. These materials are commonly referredto as “middle notes” or “base notes”. Highly skilled perfumers areusually employed to carefully blend perfume raw materials so that theresultant fragrance oils have the desired overall fragrance characterprofile. The desired overall character is dependent both upon the typeof composition in which the fragrance oil will finally be used and alsothe consumer preference for a fragrance.

In addition to the volatility, another important characteristic of aperfume raw material is its olfactory detection level, otherwise knownas the odor detection threshold (ODT). If a perfume raw material has alow odor detection threshold, only very low levels are required in thegas phase, or air, for it to be detected by the human, sometimes as lowas a few parts per billion. Conversely, if a perfume raw material has ahigh ODT, larger amounts or higher concentrations in the air of thatmaterial are required before it can be smelt by the user. The impact ofa material is its function of its gas phase or air concentration and itsODT. Thus, volatile materials, capable of delivering large gas-phaseconcentrations, which also have low ODTs, are considered to beimpactful. To date, when developing a fragrance oil, it has beenimportant to balance the fragrance with both low and high volatility rawmaterials since the use of too many high volatility materials could leadto a short lived, overwhelming scent. As such the levels of high odorimpact perfume raw materials within a fragrance oil have traditionallybeen restricted.

As used herein the term “fragrance oil” relates to a perfume rawmaterial, or mixture of perfume raw materials, that are used to impartan overall pleasant odor profile to a composition, preferably a cosmeticcomposition. As used herein the term “perfume raw material” relates toany chemical compound which is odorous when in an un-entrapped state,for example in the case of pro-perfumes, the perfume component isconsidered to be a perfume raw material, and the pro-chemistry anchor isconsidered to be the entrapment material. In addition “perfume rawmaterials” are defined by materials with a ClogP value preferablygreater than about 0.1, more preferably greater than about 0.5, evenmore preferably greater than about 1.0. As used herein the term “ClogP”means the logarithm to base 10 of the octanol/water partitioncoefficient. This can be readily calculated from a program called“CLOGP” which is available from Daylight Chemical Information SystemsInc., Irvine Calif., USA. Octanol/water partition coefficients aredescribed in more detail in U.S. Pat. No. 5,578,563.

Examples of residual “middle and base note” perfume raw materialsinclude, but are not limited to, ethyl methyl phenyl glycidate, ethylvanillin, heliotropin, indol, methyl anthranilate, vanillin, amylsalicylate, coumarin. Further examples of residual perfume raw materialsinclude, but are not limited to, ambrox, bacdanol, benzyl salicylate,butyl anthranilate, cetalox, ebanol, cis-3-hexenyl salicylate, lilial,gamma undecalactone, gamma dodecalactone, gamma decalactone, calone,cymal, dihydro iso jasmonate, iso eugenol, lyral, methyl beta naphthylketone, beta naphthol methyl ether, para hydroxylphenyl butanone,8-cyclohexadecen-1-one, oxocyclohexadecen-2-one/habanolide, florhydral,intreleven aldehyde.

Examples of volatile “top note” perfume raw materials include, but arenot limited to, anethol, methyl heptine carbonate, ethyl aceto acetate,para cymene, nerol, decyl aldehyde, para cresol, methyl phenyl carbinylacetate, ionone alpha, ionone beta, undecylenic aldehyde, undecylaldehyde, 2,6-nonadienal, nonyl aldehyde, octyl aldehyde. Furtherexamples of volatile perfume raw materials include, but are not limitedto, phenyl acetaldehyde, anisic aldehyde, benzyl acetone, ethyl-2-methylbutyrate, damascenone, damascone alpha, damascone beta, flor acetate,frutene, fructone, herbavert, iso cyclo citral, methyl isobutenyltetrahydro pyran, isopropyl quinoline, 2,6-nonadien-1-ol,2-methoxy-3-(2-methylpropyl)-pyrazine, methyl octine carbonate,tridecene-2-nitrile, allyl amyl glycolate, cyclogalbanate, cyclal C,melonal, gamma nonalactone, c is 1,3-oxathiane-2-methyl-4-propyl.

Other useful esidual “middle and base note” perfume raw materialsinclude, but are not limited to, eugenol, amyl cinnamic aldehyde, hexylcinnamic aldehyde, hexyl salicylate, methyl dihydro jasmonate,sandalore, veloutone, undecavertol, exaltolide/cyclopentadecanolide,zingerone, methyl cedrylone, sandela, dimethyl benzyl carbinyl butyrate,dimethyl benzyl carbinyl isobutyrate, triethyl citrate, cashmeran,phenoxy ethyl isobutyrate, iso eugenol acetate, helional, iso E super,ionone gamma methyl, pentalide, galaxolide, phenoxy ethyl propionate.

Other volatile “top note” perfume raw materials include, but are notlimited to, benzaldehyde, benzyl acetate, camphor, carvone, borneol,bornyl acetate, decyl alcohol, eucalyptol, linalool, hexyl acetate,iso-amyl acetate, thymol, carvacrol, limonene, menthol, iso-amylalcohol, phenyl ethyl alcohol, alpha pinene, alpha terpineol,citronellol, alpha thuj one, benzyl alcohol, beta gamma hexenol,dimethyl benzyl carbinol, phenyl ethyl dimethyl carbinol, adoxal, allylcyclohexane propionate, beta pinene, citral, citronellyl acetate,citronellal nitrile, dihydro myrcenol, geraniol, geranyl acetate,geranyl nitrile, hydroquinone dimethyl ether, hydroxycitronellal,linalyl acetate, phenyl acetaldehyde dimethyl acetal, phenyl propylalcohol, prenyl acetate, triplal, tetrahydrolinalool, verdox,cis-3-hexenyl acetate.

In the past, many attempts have been made to delay the volatilityprofiles of fragrance oils within many types of compositions to extendthe overall fragrance effect. For instance the fragrance oil may beformulated to include a higher proportion of perfume raw materials witha low volatility and which are therefore more substantive on thesubstrate. This may restrict the fragrance character that can beachieved over time. Another approach has been to chemically, andreversibly, modify the perfume raw materials to a pro-perfume compoundwhich is disclosed in patent applications WO 98/47477; WO 99/43667; WO98/07405; WO 98/47478; all of which are incorporated herein byreference. The resultant pro-perfumes are not themselves volatile but,after the chemical modification is reversed, usually by hydrolysis uponapplication to the substrate, the perfume raw material is released andcan then evaporate in the usual way. In these examples the release rateof the perfume raw materials is controlled by the reaction rate of thepro-perfume to perfume raw material transformation.

Olfactory-active substances comprise compositions comprising compounds,mixtures or suspensions of odorous compounds that neutralize, cover oreliminate odors. For example, cyclodextrins are effective at providingodors and also at trapping odors, which may neutralize or eliminate anexisting odor. Repellents may be one or more compounds that repel otherorganisms, such as insects. For example, compositions made from naturaloils are found to be excellent insect repellents. See U.S. PatentApplication Pub. No. 2007/0224232, which is incorporated in itsentirety, for examples of effective insect repellent compositions.

A fragrance composition may be one compound or a mixture or suspensionof one or more compounds, and the present invention comprises one ormore of such fragrance compositions. An aspect of an article comprisesother compositions, which may be used with fragrance compositions or inplace of fragrance compositions and comprises compositions comprisingodorous substances such as those used as air fresheners, sanitizers, ordeodorizers, or compounds which remove odors, including but not limitedto, cyclodextrins and compounds which bind to hydrophobic compounds thatcause odors. An example of such a composition is sold as Febreeze® whichinclude a modified starch compound An olfactory-active substancecomposition may comprise a material, such as a volatile material,including but not limited to fragrance, perfume, essential oil, solvent,deodorizer, malodor counteractant, insect repellant, and have scentingor perfumery activity alone or in combination with antimicrobial,insecticide, or pesticide activity. At least a portion of theolfactory-active substance composition is released when an article isexposed to ambient air. For example, a portion of an olfactory-activesubstance composition such as a fragrance is released when an article isexposed to ambient air.

An olfactory-active composition may be provided in an organic solvent,such as alcohol or an oil, may be provided in a mixture of organic andaqueous solvents, or may be provided in aqueous solvents such as water,saline or physiological salts. An olfactory-active composition maycomprise an odorous compound or fragrance compound that may be modified,such as by chemical attachment of a substituent group, salt formation,crystal formation, or other chemical or physical change to the compound,to alter the activity of the compound, such as to alter its release ratefrom an article, maintenance of the compound in a volatile state,maintenance or release of the compound in the article, maintenance orrelease of the compound in the air, and maintenance or release of thecompound in its solvent. Modified compounds may be used for detection ofthe presence of the olfactory-active composition in an environment, orfor measuring the concentration of an olfactory-active composition or acomponent of the composition in the olfactory-active composition, in anarticle or in an environment.

An odorous compound may be provided in an olfactory-active composition.For example, an olfactory-active composition may comprise one or morefragrances. An olfactory-active composition may comprise a solvent. Anolfactory-active composition may comprise one or more control elements,which are compounds or molecules that aid in odorous compound control,such as in release or maintenance of the odorous compounds in thesolvent or article, maintenance of the odorous compounds in the air, ormay aid in or retard the volatilization of the odorous compounds. Anexample of an olfactory-active composition odorous control element is asurfactant. Surfactants may be nonionic, anionic; cationic, orzwitterionic. One or more surfactants may be added to anolfactory-active composition and aid in the control of the release ofthe odorous compounds from the solvent solution, and ultimately, fromthe article. Control compounds may comprise compounds or molecules thatdegrade with time and once degraded, the odorous compound is more easilytransmitted to the environment. Control elements may also beincorporated in the design of an article to aid in odorous compoundcontrol such as maintenance of the odorous compound release rate.Control elements may comprise compounds incorporated into theolfactory-active composition or that are associated with the structuralcomponents. For example, waxes or starches may aid in inhibiting orcontrolling the release of an olfactory-active compound. A starch or waxmay be applied to the matrix material or the structural component, inany manner, such as covering one or more surfaces or in a particularpattern or a random pattern.

Odorous control elements may include compounds, molecules or solutionsthat affect the volatilization of the odorous compounds, mixtures orsuspensions of the olfactory-active composition. A proportion of theolfactory-active composition may be such a control element solution. Forexample, olfactory-active composition may comprise 80-85% of a fragrancein an oil solvent with 15-20% of the composition comprising hexyleneglycol.

Other compounds known in the art may be used as odorous controlelements. For example, compounds comprising at least one β-carbonate orβ-thio carbonyl moiety capable of liberating an active enone. As “activeenone” it is intended, for example, an α,β-unsaturated ketone, aldehydeor carboxylic ester capable of bringing an odor benefit or effect intoits surrounding environment, such as a perfuming ingredient, such as ina fragrance of the present invention. By “perfuming ingredient” it ismeant a fragrance compound, which may be used in the perfumery industry,for example, a compound which is used as ingredient in perfumingpreparations or compositions in order to impart a hedonic effect.

Compositions of the present invention comprise olfactory-activecompositions provided in controlled release forms, including but notlimited to, encapsulation, water-in-oil, oil-in-water emulsions,liposomes, or others. The present invention comprises encapsulation ofthe olfactory-active material in a protective coating. The protectivecoating may be a polymeric material. The polymeric material may protectthe fragrance or olfactory material from evaporation, reaction,oxidation or otherwise dissipating with time.

Methods for encapsulation of fragrances may be taught in U.S. Pat. Nos.2,800,457, 3,870,542, 3,516,941, 3,415,758, 3,041,288, 5,112,688,6,329,057, and 6,261,483, all of which are incorporated by reference asif set forth in their entirety. Other methods of fragrance encapsulationmay be found in the Kirk-Othmer Encyclopedia. Encapsulating polymersinclude those formed from melamine-formaldehyde or urea-formaldehydecondensates, as well as similar types of aminoplasts. Capsules made viathe simple or complex coacervation of gelatin may be used. Capsuleshaving shell walls comprised of polyurethane, polyamide, polyolefin,polysaccaharide, protein, silicone, lipid, gelatins, modified cellulose,gums, polyacrylate, polyphosphate, polystyrene, and polyesters orcombinations of these materials are also contemplated for the presentinvention.

U.S. Pat. No. 4,081,384 discloses a softener or anti-stat core coated bya polycondensate suitable for use in a fabric conditioner; U.S. Pat. No.5,112,688 discloses selected fragrance materials having the propervolatility to be coated by coacervation with micro particles in a wallthat can be activated for use in fabric conditioning; U.S. Pat. No.5,145,842 discloses a solid core of a fatty alcohol, ester, or othersolid plus a fragrance coated by an aminoplast shell; and U.S. Pat. No.6,248,703 discloses various agents including fragrance in an aminoplastshell that is included in an extruded bar soap. The above U.S. patentsare hereby incorporated by reference as if set forth in their entirety.

Encapsulation of fragrance in a polymeric shell may help preventfragrance degradation and loss. Methods of aiding the deposition ofencapsulated fragrances have been disclosed. U.S. Pat. No. 4,234,627discloses a liquid fragrance coated with an aminoplast shell furthercoated by a water insoluble meltable cationic coating in order toimprove the deposition of capsules from fabric conditioners. U.S. Pat.No. 6,194,375 discloses the use of hydrolyzed polyvinyl alcohol to aiddeposition of fragrance-polymer particles from wash products. U.S. Pat.No. 6,329,057 discloses use of materials having free hydroxy groups orpendant cationic groups to aid in the deposition of fragranced solidparticles from consumer products.

As used herein an “entrapment material” is any material which, afterapplication of the composition to a substrate, suppresses the volatilityof the perfume raw materials within the fragrance oil thus delayingtheir evaporation. It is not necessary that the entrapment materialforms an association with the perfume raw material within thecomposition itself, only that this association exists on the substrateafter application of the composition. Non limiting examples ofmechanisms by which the delay in evaporation may occur are by theentrapment material reversibly or irreversibly, physically or chemicallyassociating with the perfume raw material through complexing,encapsulating, occluding, absorbing, binding, or otherwise adsorbing theperfume raw materials of the fragrance oil.

As defined herein “reversible entrapment” means that any entrapmentmaterial: perfume raw material association in which the association canbe broken down so that the entrapment material and perfume raw materialsare released from each other. As defined herein “irreversibleentrapment” means that the entrapment material: perfume raw materialassociation cannot be broken down. As defined herein “chemicallyassociated” means that the entrapment material and perfume raw materialare linked through a covalent, ionic, hydrogen or other type of chemicalbond. As defined herein “physically associated” means that theentrapment material and perfume raw material are linked through a bondwith a weaker force such as a Van der Waals force. Highly preferred isthat, upon the substrate, the entrapment material and the perfume rawmaterial form a reversible physical or chemical association.

Entrapment materials for use herein are selected from polymers;capsules, microcapsules and nanocapsules; liposomes; pro-perfumes; filmformers; absorbents; cyclic oligosaccharides and mixtures thereof.Preferred are pro-perfumes, absorbents and cyclic oligosaccharides andmixtures thereof. Encapsulating polymers include those formed frommelamine-formaldehyde or urea-formaldehyde condensates, as well assimilar types of aminoplasts. Additionally, capsules made via the simpleor complex coacervation of gelatin are also preferred for use with thecoating. Capsules having shell walls comprised of polyurethane,polyamide, polyolefin, polysaccaharide, protein, silicone, lipid,gelatins, modified cellulose, gums, polyacrylate, polyphosphate,polystyrene, and polyesters or combinations of these materials are alsofunctional.

On the substrate, where the perfume raw material and the entrapmentmaterial exist in an associated form, the weight ratio of high odordetection perfume raw material to entrapment material within theassociated form may be in the range from about 1:20 to about 20:1, fromabout 1:10 to about 10:1, in the range from about 1:7 to about 7:1, inthe range from about 1:5 to about 5:1, from about 1:3 to about 3:1 andin the range from about 1:2 to about 2:1.

Release of fragrance by article of the present invention may becontrolled by one or more methods described herein. There are manymethods described herein for controlling fragrance release and one ormore of those methods may be used in any one article. The amount offragrance contained by the article may control the period of time thatfragrance is released into the environment in which the article isplaced. Other methods or elements for controlling fragrance release ormaintenance in an environment include, but are not limited to, thechemical compounds of the one or more fragrances used; modifications toone or more chemical compounds; other compounds in the fragrancecomposition including the fragrance solvent, surfactants, compoundsknown to affect the absorption or release rate of the fragrancecompounds; the characteristics of the matrix material; how the matrixmaterial is formed into a structural component; treatments to the matrixmaterial such as coatings applied to the matrix; when in the treatmentschema, if any, of the matrix material the fragrance composition isadded to the matrix material; the formation of the structural component,and treatments to the structural component such as shaping it orapplication of coatings to all or a portion of the surface of thestructural component.

An article of the present invention may change color in all or a portionof the structural component to indicate the amount of olfactory-activecomposition present in the structural component. For example, acomposition comprising a color change indicator is incorporated into thestructural component and after release of substantially all of theolfactory-active composition, the indicator changes color. Examples of acolor change indicator includes but is not limited to, an organic dye,food grade dye, or mixtures thereof, FD&C Blue No. 1, FD&C Blue No. 2,FD&C Green No. 3, FD&C Red No. 40, FD&C Red No. 3, FD&C Yellow No. 5,FD&C Yellow No. 6, Solvent Red 24, Solvent Red 26, Solvent Red 164,Solvent Yellow 124, Solvent Blue 35, methyl violet, eosin yellow,malachite green, thymol blue, methyl yellow, bromophenol blue, congored, methyl orange, bromocresol green, methyl red, litmus, bromocresolpurple, bromophenol red, bromothymol blue, phenol red, neutral red,naphtholphthalein, cresol red, phenolphthalein, thymolphthalein, alkaliblue, Alizarin Yellow R, indigo carmine, epsilon blue, or mixturesthereof. The color change indicator may be responsive to pH.

An article of the present invention may be packaged for storage ordelivery and sale. An article may be packaged to preserve anolfactory-active composition and to control release of anolfactory-active composition by preventing contact by ambient air. Manytypes of packaging material are capable of protecting article of thepresent invention. An aspect uses packaging materials through which anolfactory-active composition does not substantially diffuse orevaporate. Suitable materials for packaging an article includecellophane, polypropylene, some plastics, PET, polymers, fluorinatedpolyethylene, metalized films, metal, glass, glazed ceramics, and anyother impervious material. A useful packaging material includes, but isnot limited to, bi-oriented polypropylene, PET, or cellophane.

Article of the present invention may include an attachment element forattaching an article to another article or to other objects. Such anattachment element may comprise a hook, clip, or other means forattaching an article to a surface, another article, or anotherstructure. For example, an article may have an attachment element thatcomprises a portion that attaches directly to the structural componentand a portion that can be attached by a clip, hook, enclosed circle,hook and eye means (like Velcro®), string, prongs, loop, or adhesive toa surface, article or other structure such as a portion of a car, afixture in a home or office, or a body. It is also useful for attachmentelements to be shaped so that the structural component or article may beremoved and replaced with a fresh structural component or article whenthe user so desires, whether or not the attachment element is removedfrom its attached site. Multiple structural components or article may beheld in one attachment element. An article may be shaped to fit with anattachment element, such as by cutting, crimping, bending, shaping, etc.An attachment element may be used to hold or insert an article into anenvironment. For example, an attachment element may be a spike to whichan article is attached and the combined attachment element/article isplaced in a vase of flowers, or a bouquet, or into the dirt of a pottedplant.

An article of the present invention may be placed in individual ormultiple holders. A holder is a container in which an article may beplaced. The use of such a holder may be beneficial to prevent contactbetween one or more article and other surfaces. Materials which areuseful for a holder may not absorb an olfactory-active composition.Suitable materials for this include metal, ceramic, glass, plastic, andpolymers. Materials that might not be otherwise suitable can be madesuitable by coating at least a portion of the holder with a barrier thatprevents contact between the holder and the article. The holder may becapable of holding one or more article. For holders capable of holdingone or more article, one or more article with the same olfactory-activecomposition or with different olfactory-active composition may be placedinto the holder at the same time.

A holder may comprise a container having at least one perforatedsurface. The perforated surface, meaning a surface having one or moreapertures through which an olfactory-active composition can transit, maybe made of any material, and for example, may be a wire mesh. One ormore article are held by the holder and an olfactory-active compositionis released from the one or more article. The olfactory-activecomposition may be released from the entire surface of the article,including the surface of the article located within the holder. Anolfactory-active composition is transmitted through the one or moreapertures of the holder and released to the environment.

For example, where an article is a rod-shaped structural componentcomprising an olfactory-active composition, one or more of the rodarticle are placed within a holder having at least one aperture. Anolfactory-active composition is released from the rod throughout thelength of the rod, and through the one or more apertures of the holder,so that an olfactory-active composition is not trapped within theholder. This is in contrast to a reed diffuser, which comprises woodenreeds standing in a container of scented oil. The fragrance can only bereleased from the upper portion of the reed as the oil is wicked up thereed. The container does not provide any fragrance release, and merelycontains the liquid scented oil. Holders of the present invention maycomprise decorative elements or attachment elements. Holders of thepresent invention may comprise other elements, such as heaters, fans,solar panels, be powered by electricity, or have moveable parts.

A holder may be used for one or more article that comprise a slidable ormovable member for covering one or more apertures in a holder. Forexample, the holder may be a container having at least one side orsurface that is perforated and has apertures through which anolfactory-active composition is transmitted. The holder may compriseanother surface that moves or slides so as to cover the apertures andprevent an olfactory-active composition from transmitting through theholder. The slideable surface may be activated so that the apertures arenot covered and an olfactory-active composition is transmitted. Theslidable surface may remain in the open position or may be returned tothe closed aperture position depending on the desired outcome. Such aslideable or moveable section or surface may provide an adjustablerelease rate control element for an olfactory-active composition.

The present invention comprises methods for using article for providingfragrance to an enclosed environment. Methods of the present inventioncomprise using an article to provide an olfactory-active composition toa contained space, such as a room, vehicle interior, an office, adresser drawer, or a closet. Methods of the present environment compriseproviding an olfactory-active composition to an area surrounding thearticle, which may or may not be an enclosed area. For example, anarticle may be worn as a personal body adornment and provide anolfactory-active composition to the person wearing it continuously, maybe carried in a bouquet of flowers, or worn unseen to provide an odorouscomposition or odor neutralizing composition to the person.

In general, aspects of the present invention comprises articles,compositions and methods for making and using such articles andcompositions. The present invention comprises a scented article,comprising, at least one olfactory-active composition, a structuralcomponent comprising an absorbent matrix material, and a coatingcomposition covering a portion of the structural component, wherein atleast one olfactory-active composition is releasably retained in theabsorbent matrix material. The article comprising the absorbent matrixmaterial is a pulp composition. Thee absorbent matrix material may be asheet of porous paper wound about a central axis to form a multilayeredpaper rod. The wound paper may form a chamber through the central axisof the rod that is hollow and open at both ends. The chamber formedalong the central axis of the rod may be filled with a gel or liquid.The absorbent matrix material has a void volume of about 1 mL to about10 mL per structural component, depending on the matrix material. Thearticle may have an absorbent matrix material that has a void volume ofabout 1.0% to about 99% of the total volume of the structural componentThe gel or liquid comprises at least one olfactory-active composition.The coating covers more than 50% of the structural component. Thecoating covers substantially all of the structural component. Thecoating composition comprises a wax, soy wax, paraffin, bees wax,polyethylene wax, microcrystalline wax, waxes that soften or melt at atemperature greater than about 150 F, acrylates,polylactide,polyglycolide or polycaprolactone, or a polyester copolymer selectedfrom poly(lactide/glycolide) acid (PLGA) orpoly(lactid-co-.epsilon.-caprolact-one) (PLCL), alkyl- oralkoxyalkyl-2-cyanoacrylates such as n-butyl-2-cyanoacrylate or2-methoxybutyl-2-cyanoacrylate, crosslinked cyanoacrylate, polylacticacid, polyglycolic acid, lactic-glycolic acid copolymers,polycaprolactone, lactic acid-caprolactone copolymers,poly-3-hydroxybutyric acid, polyorthoesters, polyalkyl acrylates,copolymers of alkylacrylate and vinyl acetate, polyalkyl methacrylates,and copolymers of alkyl methacrylates and butadiene; and plasticizerssuch as dioctyl phthalate, dimethyl sebacate, trethyl phosphate, tri(2-ethylhexy) phosphate, tri(p-cresyl)phosphate, glyceryl triacetate,glyceryl tributyrate, diethyl sebacate, dioctyl adipate, isopropylmyristate, butyl stearate, lauric acid, dibutyl phthalate, trioctyltrimellitate, and dioctyl glutarate, Krylon® Triple-Thick crystal clearglaze.

The present invention comprises methods for making scented articles. Amethod for making a scented article comprises a) adding at least oneliquid olfactory-active composition and at least one matrix material orat least one structural component, to a closed container; and in noparticular order, b) applying a vacuum to the closed container andmaintaining the vacuum for a period of time before releasing the vacuum;and c) pressurizing the closed container and maintaining the pressurefor a period of time before releasing the pressure. Steps b) and c) maybe repeated, may be repeated at least once. Applying a vacuum comprisesa vacuum from about 0.001 mm Hg to about 700 mm Hg. Pressurizing theclosed container comprises a pressure from about 10 to about 40 psi. Theperiod of time for the vacuum or the pressure is from 1 minute to 10hours. The olfactory-active composition comprises at least one of afragrance, repellant, odor eliminating compound, aromatherapy compound,natural oil, water-based scent, odor neutralizing compound, orcyclodextrin. A sufficient amount of an olfactory-active compositioncomprises an amount that covers substantially all of the at least onestructural component. The method may further comprise removing the atleast one matrix material or at least one structural component from theclosed container. The structural component comprises a sheet ofabsorbent paper wound about a central axis to form a multilayered paperrod. The portion of the olfactory-active composition that is absorbed bythe structural component is from 2 to 200 mL.

A method for making a scented article may comprise a) adding at leastone liquid olfactory-active composition and at least one matrix materialor at least one structural component to a closed container; andoptionally, b) applying a vacuum to the closed container and maintainingthe vacuum for a period of time before releasing the vacuum; or c)pressurizing the closed container and maintaining a pressure for aperiod of time before releasing the pressure. Step b) or step c) isrepeated, is repeated at least once. Both steps b) and c) may berepeated at least once. The method may comprise only applying a vacuum.The method may comprise only applying a pressure. The method maycomprise applying both a vacuum and a pressure. Applying a vacuumcomprises a particular vacuum from about 0.001 mm Hg to about 700 mm Hgor an increasing or decreasing range of a series of vacuum values fromabout 0.001 mm Hg to about 700 mm Hg. Pressurizing the closed containercomprises a particular pressure from about 10 to about 40 psi, or anincreasing or decreasing range of a series of pressure values from about10 to about 40 psi. The period of time for the vacuum or the pressure isfrom 1 minute to 10 hours. The olfactory-active composition comprises atleast one of a fragrance, repellant, odor eliminating compound,aromatherapy compound, natural oil, water-based scent, odor neutralizingcompound, or cyclodextrin. A sufficient amount of an olfactory-activecomposition comprises an amount that covers substantially all of the atleast one structural component. The method may further comprise removingthe at least one matrix material or at least one structural componentfrom the closed container. The structural component may comprise a sheetof absorbent paper wound about a central axis to form a multilayeredpaper rod. The portion of the olfactory-active composition that isabsorbed by the structural component may be from 2 to 200 mL.

The methods of making an article may result in a scented article,comprising, at least one olfactory-active composition, a structuralcomponent comprising a matrix material of extruded or molded pulpcomposition, wherein the at least one olfactory-active composition isreleasably retained in the absorbent material. The article may furthercomprise a coating covering a portion of the structural component. Thepulp composition further comprises nanofibers. The pulp composition isextruded. The pulp composition is molded. The pulp composition furthercomprises additives.

It must be noted that, as used in this specification and the appendedclaims, the singular forms “a”, “an”, and “the” include plural referentsunless the context clearly dictates otherwise. All patents, patentapplications and references cited herein and included herein arespecifically incorporated by reference in their entireties.

It should be understood, of course, that the foregoing relates only toexemplary embodiments of the present invention and that numerousmodifications or alterations may be made therein without departing fromthe spirit and the scope of the invention as set forth in thisdisclosure.

EXAMPLES Example 1 An Exemplary Method of Making an Article

Loading procedure for the Large-Tube loading apparatus using loadingresults for nC12 and nC16.

The large tube loading apparatus has a main body that is a tube 18inches long, with an internal diameter of 1.5 inches. It holds 30 0.23″rods up to 12 inches in length. It is equipped with threaded ends toallow capping with threaded plugs. The plugs have fittings, gauges andvalves, used to provide the means to deliver and remove liquids as wellas apply vacuum or pressure to the apparatus.

The top plug has a “cross” fitting that includes two ball valves and agauge selected to register vacuum (to 30 inches of Hg) and pressure (to100 psi). One ball valve has a barbed fitting to attach a vacuum pump,while the other ball valve has a Schrader valve stem to allowpressurization with a tire pump or compressor equipped with a tirefitting.

The bottom plug has a ball valve to allow introduction and removal ofliquid to/from the device.

Thirty structural components made from paper from Plant D (referred toby letter D in examples), made as a continuous rolled paper rod,9.5″-long, and approximately 0.2335″ in diameter, were loaded withfragrance composition or a test organic solution mimicking a fragrancecomposition as follows:

-   -   Inserted structural components in the Large-Tube loading        apparatus and sealed.    -   Pumped for 15 min at a vacuum <30 in Hg. Closed the valve        connecting to the vacuum pump and observed vacuum gauge, for        leaks.    -   If no significant leaks were observed, began introducing liquid        (fragrance composition) by opening the bottom valve connected to        the liquid reservoir. It took about 350 mL of liquid to        completely cover the structural components. Once the liquid        covered the structural components, stop the liquid flow. The        vacuum should be between 25-30 in Hg.    -   Significant outgassing may be observed depending on the liquid        boiling point. Some low-boiling point materials may “boil off”        and contaminate the vacuum pump oil, thus, a cold vacuum trap        was used to prevent damage to the pump.    -   Kept the liquid-filled container under vacuum for an additional        5 minutes to allow any entrapped gas remaining in the rods or        liquid to escape.    -   Pressurized the liquid-filled loading apparatus to 40 psi for 15        minutes.    -   Released the pressure, and under atmospheric pressure, opened        the bottom valve connected to the liquid reservoir. Allowed the        liquid to drain into the liquid reservoir.    -   The liquid remaining in the loading apparatus can be drained by        applying slight air pressure, e.g., 5-10 psi, and blowing the        liquid into a suitable container    -   After eliminating excess liquid, removed the structural        components, now loaded with fragrance composition, from the        loading container. They should be near-dry to the touch, and        leave a faint liquid residue on an absorbent towel.        Alternatively, a smaller apparatus was used.    -   Loading of a small-volume apparatus constructed from a 12″-long,        ½″ pipe, PVC nipple, 2″ extension, caps, and an automobile tire        valve stem.

The tube holds 5 structural components made from paper from Plant D,made as a continuous rolled paper rod cut to 4.75″ length, requiredapproximately 25-30 mL of liquid. It was pumped down without liquid byremoving the Schrader valve from the tire valve stem. Structuralcomponents were weighed after pumping down to ascertain the amount ofmoisture they held. After pump-down, the container was opened to theair, and then filled with liquid olfactory-active composition using agas-tight syringe equipped with a Teflon tube (0.3 mm id). The Schradervalve was replaced in the stem; the container was capped, andpressurized to 30-40 psi.

Table 1 below shows results obtained with five half-rods loaded withnC12 using the small loader

TABLE 1 rod # L, in weight 10′ vac Δ weight moisture Load g Total g %load I 4.80 2.8580 2.8183 0.0397 1.4% 3.8488 1.0305 37% II 4.78 2.85132.8425 0.0088 0.3% 3.8560 1.0135 36% III 4.79 2.8492 2.8113 0.0379 1.3%3.9092 1.0979 39% IV 4.79 2.8707 2.8615 0.0092 0.3% 3.8873 1.0258 36% V4.78 2.8872 2.8562 0.0310 1.1% 3.8885 1.0323 36% pumped for ca30 min, in12 in ½″ pipe pressurized to 20 psi after loading with 35 mL of C12Average 36.7%  

The fourth column, labeled 10′ vac, shows the weight of the rods afterpumping down for ten minutes. The weight loss, attributed to moistureranges from 0.3 to 1.4%. The large % error was attributable to the waythe experiment was performed. The average load is 36.7%.

Results obtained using the Large-Tube loading apparatus are shown belowin Table 2 for two loadings of nC12.

TABLE 2 # total, loaded, gain, Load rods g g g % run#1 30 169 233 6437.9% run #2 30 169 232 63 37.3%Agreement was within experimental error of the balance used to acquirethe data. The results were also in agreement with those obtained usingthe small loader (ave 37.6% vs. 36.7%).

Table 3 below shows results of loading 5 half-rods (4.75″) with nC16.The table includes a second step of removing surface liquid.

TABLE 3 First blotting to dry second blotting to dry surface surface rod# L, in Wt (g) loaded total % load loaded total % load A 4.579 2.66043.7354 1.0750 40.4% 3.7269 1.0665 40.1% B 4.603 2.7234 3.7884 1.065039.1% 3.7823 1.0589 38.9% C 4.594 2.7641 3.7986 1.0345 37.4% 3.79721.0331 37.4% D 4.592 2.7060 3.7984 1.0924 40.4% 3.7913 1.0853 40.1% E4.597 2.7354 3.8175 1.0821 39.6% 3.8151 1.0797 39.5% Average 39.4%Average 39.2%

Interestingly, the C16 data showed an average loading of 39.3% asopposed to 36.7% for n-C12. The difference cannot be explained bydensity difference alone (C16=0.774 g/mL vs. C12=0.754 g/mL, at roomtemperature). The results obtained using the Large-Tube loadingapparatus for nC12 and C16 are shown below along with the density andvolume calculation.

TABLE 4 # total, g loaded, g gain, g load % nC12 run 30 169 233 64 37.9%#1 run 30 169 232 63 37.3% #2 nC16 30 169 235 66 39.1% VolC16 85.3 mLDensity of nC16 at room 0.774 temperature. Density of nC12 at room 0.754VolC12 84.2 mL temperature.

Note that the loadings with the small and Large-Tube loading apparataeshowed the same trend: loadings of nC12 were smaller than those achievedwith nC16. The difference was small, and was approximately 1 mL out of85 mL or about 1.2%. The total volume, calculated for 30 structuralcomponents, 9.5″-long and 0.2335″ diameter is 200.6 mL, thus, 85.3 mLrepresents a “void” or “accessible” volume of 42.5%.

Example 2

Observations and loading procedures for nC12, nC16 and Douglas Firperfume into 9.5″ rolled paper rods from paper from Plant D

Loading procedure for Douglas Fir Perfume.

The loader, of Example 1 was modified by the installation of a tire stemand Schrader valve.

Thirty rolled paper rods 9.5″-long, 0.2335″ dia, paper from Plant D,weighing 171.6 grams as received, were introduced to the large loaderand loaded with Doulas Fir olfactory-active composition and the endsealed. Sealing of the apparatus is problematic, but is best done bywrapping the ends with a Teflon tape strip sufficiently long to wraparound the threaded-end six times. The loader is pressurized to about 40psi and soap water used to test for leaks. If bubbles are detected, moreTeflon tape needs to be used to fix the leak.

No leaks were detected, the loader was pumped down to a vacuum >30 in.Hg for 45 minutes. The pump is a two-stage, 3 cfm pump equipped with atrap kept at water-ice temperature. At 45 minutes, the vacuum pump wasisolated by turning off the valve connecting the loader to the pump. Theperfume was loaded in a clear graduated container connected to thebottom valve of the loader. The graduated container showed a volume of450 mL. The bottom valve was opened carefully to introduce the perfumeinto the loader. Significant bubbling was observed. The bottom valve wasturned off and the bubbling was allowed to subside. More liquid wasintroduced, by opening the bottom valve, until the rods tops werecovered, and about one inch of liquid remained over the tops. At thispoint the vacuum was about 25 in. Hg. The loader was left under vacuumfor 5 minutes. The liquid level dropped to about 0.5″ above the rodstops. This level drop suggests liquid is being absorbed by the rodswhile the loader was under vacuum. More perfume was introduced and morebubbles were released. The final level was set at 3 inches above therods tops, and the vacuum was measured at 20 in. Hg. At this point 385mL of perfume composition was loaded into the loader.

The loader was pressurized to 44 psi and the liquid level dropped about0.2″. Initially, the pressure dropped with time, requiringre-pressurizing every about 2-3 minutes, having dropped 2-3 psi duringthat time. However, after 20 minutes the pressure stabilized, droppingabout 1 psi in 15 minutes. The system was left under pressure for 3hours.

After the pressurized period, the Schrader valve was used to relieve thepressure and drain most of the liquid by opening the bottom valve. Theliquid was removed from the container prior to the next step. Afterclosing the valve, the container was pressurized back to 40 psi. Excessliquid was drained by slightly opening the bottom valve. This processwas repeated four times before removing the rods from the container.

Results.

The initial weight of 30 rods of paper from Plant D was 171.6 grams.After loading the rods weighed 244.5 g, or a loading by weight of 42.5%.The density of this perfume was measured at 0.879, thus, the free volumeor available volume in the rods is calculated at 82.9 mL.

Loading Procedure for nC12 and nC16.

Thirty rods paper from Plant D 9.5″-long, and about 0.2335″ in diameter,weighing 169 grams as received, were introduced to the loader and theend sealed. In these experiments weight was determined with a scale thatonly weighed to the nearest gram, as opposed to the scale used tomeasure loadings with the Douglas fir perfume.

The loader was pumped down for 15 min to a vacuum <30 in Hg. No trap wasused. The pump was isolated by closing the valve connecting the pump tothe loader. The vacuum should hold for a few minutes if there are nosignificant leaks. No significant leaks were observed, and beganintroducing liquid by opening the bottom valve connected to the liquidreservoir. Once the liquid covered the rods, the bottom valve was closedto stop the liquid flow. The vacuum should still be between 25-30 in Hg.Kept the liquid-filled loader under vacuum for 5 additional minutes toallow any entrapped gas remaining in the rods or liquid to escape.

Pressurized the liquid-filled loader to 40 psi for 15 minutes. Releasedthe pressure, and under atmospheric pressure, opened the bottom valveconnected to the liquid reservoir. The liquid drained into the liquidreservoir.

The liquid remaining in the loader was drained by applying slight airpressure, e.g., 5-10 psi, and blowing the liquid into a suitablecontainer.

After eliminating excess liquid, removed the rods form the loadingcontainer. They should be near-dry to the touch.

Results

The initial weight of 30 rods of paper from Plant D was 169 grams. Thedifference in this weight and the one reported for the Douglas Firexperiment above reflects the use of a different balance to obtain thehydrocarbon data. After loading the rods with nC12, the results ofduplicate runs showed weights of 232 and 233 g. Thus, the load of nC12averages 37.5% by weight, or a “free or available” volume of 84.2 mLassuming a density of 0.754 g/mL. After loading the rods with nC16, therods weighed 235 g. Thus, the load is 39.1% by weight, or a “free oravailable” volume of 85.3 mL assuming a density of 0.774 g/mL.

Example 3 Summary of Release Data Obtained Using a Rapid-Testing Box andRods Loaded with N-hydrocarbons

A Plexiglas box, was evaluated for applicability to the study of perfumerelease from rods of paper from Plant D. The Plexiglass box is about1-foot tall, 1-foot wide, and about 6 inches deep. It has three fans onone side, each moving about 10 cfm, while the opposite side is left openbut covered with a window screen to act as a diffuser, and to preventparticulate matter from entering the box. The box has a hinged frontdoor and leveling screws.

The box has 8 small holes on the top, allowing the insertion of wirehooks used to suspend rods. The hooks were fixed in place with aluminumduct tape. The rods were fitted with a small cap and hung in the box.The rod numbers reflect the position within the box, i.e., 1 is farthestfrom the fans, and so on.

Two sets of rods were used. One set has a load of 37.5% w/w of n-C12,while the other has a 39.1% w/w load of C16. The difference in loading,by weight, likely reflects the density difference between those twomaterials. The loading procedure used was described in Examples 1 and 2.Two 9.5″ rods were removed from each set and cut in half. The resultingtwo sets of four 4.7 in-long rods were fitted with caps and labeled 1-4for nC16 and 5-8 for nC12. The half-rods hold a load of about 1.15 g ofhydrocarbon each. They were hung inside the box in the order1,5,2,6,3,7,4 and 8, alternating from C16 to C12, to determine if therewere any positional effects. Weight losses as a function of time insidethe box were recorded using a 4-place analytical balance, with arepeatability of +0.1 mg. The dimensions of the analytical balancedetermined the choice to use 4.7″ rods.

Results.

Rods loaded with n-C12

Loss data for the first 22 hours inside the box, for nC12-loaded 4.7″rods, is shown below in tabular and graphical form, Table 5 and FIG. 3weights in grams and time in hours. Thus, after only 22 hours, about 70%of the estimated load has been released to the air (0.80/1.15).

TABLE 5 Time, Hrs. 1 3 5 17 22 C12-5 −0.0431 −0.1258 −0.2037 −0.6387−0.7855 C12-6 −0.0430 −0.1279 −0.2090 −0.6817 −0.7961 C12-7 −0.0409−0.1122 −0.1814 −0.5878 −0.7458 C12-8 −0.0533 −0.1563 −0.2556 −0.7918−0.8556 Average weight −0.0451 −0.1306 −0.2124 −0.6750 −0.7958 stdev 0.0056  0.0185  0.0312  0.0868  0.0454 rel stdv −12% −14% −15% −13% −6%nC12, linearity 17 hours 4 data points time, h wght loss calc RegressionStatistics 1 −0.0451 −0.05059 Multiple R 0.999864 3 −0.1306 −0.12883 RSquare 0.999729 5 −0.2124 −0.20708 Coefficients StdError 17 −0.6750−0.67655 Intercept −0.01146 0.0040998 22 −0.7958 −0.87217 X, g/H−0.03912 0.0004555

The linearity of the nC12 release over the first 17 hours stronglysuggests the nC12 is being released from the rod as if it was animmobilized liquid. The slope shown (X variable in the regression tableabove) is 39.1 mg/hour/rod.

The last data point, 22 hours, shows deviation from linearity. Thoughnot wishing to be bound by any particular theory, it is theorized thatat this point, a different release mechanism took place.

Example 4 Summary of Release Data Using Coated and Un-Coated Rods ofPaper from Plant D Loaded with n-C12

The Plexiglas box, of Example 3 was used to study the release profile ofcoated and un-coated rods of paper from Plant D loaded with n-C12.

Several Coatings Sufficiently Thick (or Efficient) to Reduce the ReleaseRate of Rods were Tested.

In one example, the rods were coated with Krylon® Triple-Thick crystalclear glaze. The results of this experiment are shown in FIG. 4 asweight loss, in grams, vs. hours.

The un-coated rods behaved as previously reported: linear loses withtime, a slope of 0.0435 grams/hour for the first 17 hours, followed byan exponential release, approaching asymptotically the material load inthe rod, about 1.15 g. The Krylon-coated rods showed a different releaserate, ranging from 0.0020 grams/hour, for the 15-48 hour period, to0.0016 grams/hour for the 48-95 hour period. Thus, there is a about 20×drop in the amount of material released from the rods.

The experiment shows the rate of release of loaded paper-based rods usedto deliver organic compounds to the air can be reduced by coating therods. The data also showed that the coating preserves the desirablelinear delivery of the rods over most of their useful life.

Example 5 Summary of Release Data Using Coated and Un-Coated Rods ofPaper from Plant D Loaded with Douglas Fir Perfume

The Plexiglas box of Example 3 was used to study the release profile ofcoated and un-coated rods of paper from Plant D loaded with Douglas Firperfume.

Nine and a half inches-long rods of paper from Plant D, loaded withDouglas Fir perfume as described in Examples 1 and 2, were cut in half.Each 4.7″ half contains about 1.2 grams of perfume. Rods labeled 1-3were left un-coated, while 4-6 were coated with Krylon, and dried in thePlexiglas box for 10 min. The rods were placed inside the box in theorder 1,4,2,5,3,6, with 1 placed farthest from the fans.

The coated rods had coating weights of 0.0440, 0.0498 and 0.0298 gramsfor rods 4,5, and 6, respectively. Assuming a uniform coating, and adensity of 1 gram/mL, the film thickness would range from 22 to 13μ.Because spraying from a can, by hand, was very unlikely to produce auniform coating on round rods, the range was only an estimate of theactual film thickness on the rods.

Results, shown in FIG. 5, represent the average weight loss of threehalf-rods (in grams) on y axis with time (hours) on the x axis.

The initial release of perfume, measured at 16-28 hours, was 0.0119 and0.0061 grams per hour for un-coated and coated 4.7″ rods, respectively.Thus, coating rods with Krylon produced a decrease in the release rateof the perfume loaded into the rods. The initial release rate is 2×smaller for the coated rods, thus, extending the lifetime of the rod.

The release rates measured after 110 hours were 0.0019 and 0.0024 gramsper hour for un-coated and coated rods, respectively. The rate for thecoated rods is greater than that for the un-coated rods, reflecting theextended “lifetime” of the rod.

Example 6 Summary Data of Rods of Paper from Plant D, Rods of Paper fromPlant F and Rods of Paper from Plant G Loaded with nC16 and Douglas FirPerfume. Loading Data: Effect of Loading Techniques on Rods of Paperfrom Plant D.

Loadings of rods of paper from Plant D, obtained using the large volumeloader or a small-volume loader of Examples 1 and 2, and a variety oftime- and vacuum/pressure-conditions, are shown in the Tables below.

TABLE 6 RODS OF PAPER FROM PLANT D C12, Small-volume loader 1.040average grams per 4.7″ rod 1.379 C12 volume (mL) 3.343 mL in 4.7″ rodvolume 41.3% occupied of “available volume” 36.7% C12 load by weight

TABLE 7 C12, Large-volume loader 1.067 average grams per 4.7″ rod 1.415C12 volume (mL) 3.343 mL in 4.7″ rod volume 42.3% occupied of “availablevolume” 37.9% C12 load by weight

TABLE 8 C12, Large-volume loader 1.050 grams per 4.7″ rod 1.393 C12volume (mL) 3.343 mL in 4.7″ rod volume 41.7% occupied of “availablevolume” 37.3% C12 load by weight

The data shown in Tables 6-8 suggested that the properties of the twoloaders and the different conditions employed to perform thoseexperiments did not change the loading achievable with nC12. The datashowed that the volume of the rods of paper from Plant D occupied byliquid is 42±1%. This percentage was constant over a wide range ofexperimental conditions.

Loading data: effect of loading nC16 and Douglas Fir into rods made withdifferent papers. Data obtained with large-volume loader

Loading data of rods of paper from Plant D with nC16 is shown below.

TABLE 9 C16 in rods of paper from Plant D 1.100 grams per 4.7″ rodrod1.421 C16 volume (mL) 3.343 mL in 4.7″ rod volume 42.5% occupied of“available volume” 39.1% C16 load by weight

The nC16 percent load by weight was larger than that measured with nC12(39.1 vs 37±1%, respectively) because of the higher density of nC16(0.774 vs 0.754 g/mL). The available volume in the rod should be aconstant determined by the matrix material structure. Once the weightloading was corrected for density, the percent occupied by volumeremains constant (42±1%), as expected.

Loading data of rods of paper from Plant D loaded with Douglas Firperfume is shown in Table 10.

TABLE 10 Douglas Fir in rods of paper from Plant D 1.215 grams per 4.7″rod 1.381 D-F volume (mL) 3.343 mL in 4.7″ rod volume 41.3% occupied of“available volume” 42.5% D-F load by weight

The Douglas Fir load by weight is larger than that measured with nC16and nC12 because it has a density of 0.88 g/mL. But, the availablevolume in the rod is 41.3%, within the expected experimental error.

Loading data of rods of paper from Plant F rods loaded with Douglas Fir(D-F) perfume is shown below

TABLE 11 Douglas Fir in rods of paper from Plant F, Type 1 1.45 gramsper half rod 1.649 D-F volume (mL) 3.343 mL in 4.7″ rod volume 49.3%occupied of “available volume” 57.8% D-F load by weight

The rods of paper from Plant F rods have a larger available volume thanthe rods of paper from Plant D (49 vs 42%, respectively). As aconsequence, their load by weight is significantly greater.

Loading data of rods of one type of paper from Plant G loaded withDouglas Fir perfume is shown below in Table 12.

TABLE 12 Douglas Fir in rods of paper from Plant G, Type 1 1.39 gramsper half rod 1.580 D-F volume (mL) 3.343 mL in 4.7″ rod volume 47.3%occupied of “available volume” 50.4% D-F load by weightLoading data of rods of paper of Type 2 from Plant G loaded with DouglasFir perfume is shown below.

TABLE 13 Douglas Fir in rods of paper from Plant G Type 2 1.46 grams perhalf rod 1.660 D-F volume (mL) 3.343 mL in 4.7″ rod volume 49.7%occupied of “available volume” 57.9% D-F load by weightThe rods of Type 2 paper from Plant G showed a larger available volumethan the Type 1 rods of paper from Plant G, and load comparably to therods of paper from Plant F.

Perforated Paper Matrix Material

To increase available volume a trial was made using perforated paper.Rods were made with paper from Plant D perforated by punching 1mm-diameter holes separated by a distance of 1 mm. The results are shownin Table 14.

TABLE 14 C16 in rods of paper from Plant D perforated with 1 mm diaholes. 1.153 grams per 4.7″ rod 1.490 C16 volume (mL) 3.343 mL in 4.7″rod volume 44.6% occupied of “available volume” 51.0% C16 load by weightPerforations achieved an increase in available volume for rods of paperfrom Plant D (44.6% vs 42±1%).

Example 7 Paper Rods Loaded by Soaking for Three Days: a Comparison ofLoads and Release Rates with Rods Loaded by Means of a Vacuum/PressureProcedure

The ability to load rods by soaking in liquids for three days wasevaluated with nC12 and Douglas Fir (D-F) perfume. Two rods types, rodsof paper from Plant D and rods of Type 2 paper from Plant G, were used.

Loading results. Results and a comparison with previous loadingsperformed by a Vacuum/Pressure (Vac-Press) procedure previouslydescribed in Examples 1 and 2, are shown in Table 17.

TABLE 15 C12 Soaking C12 Soaking D-F Soaking rods of Type 2 rods ofpaper from rods of paper rods of paper Plant G from Plant D from Plant Drods weight, 40.98 g 45.04 g 45.08 g unloaded rods weight, 60.5 g 60.5 g61.8 g loaded % loaded by 48% 34% 37% Weight load in 1.22 g 0.97 g 1.05g 4.7″ rod C12 Vac-Press C12 Vac-Press D-F Vac-Press rods of Type 2 rodsof paper from paper rods of paper Plant G from Plant G from Plant G %loaded by 55-58% 37-38% 42-43% Weight

The results show that compared to the method of Examples 1 and 2,loadings attainable by soaking for three days are lower, e.g., rods ofType 2 paper from Plant Gload 55-58% vs 48% of C12 by weight for theVacuum/Pressure and soaking procedure, respectively. Releasereproducibility. Though not wishing to be bound by any particulartheory, it is currently thought that rods loaded by soaking were notuniformly loaded and therefore showed large standard deviations indelivery rates. This was shown in Table 18 as weight loss over time(hours), for three rods of paper from Plant D (D1-3) loaded by soakingwith C12.

TABLE 16 hours 0.5 1 1.5 2 2.5 D1 −0.0245 −0.0456 −0.0666 −0.0876−0.1088 D2 −0.0209 −0.0393 −0.0584 −0.0762 −0.0937 D3 −0.0165 −0.0300−0.0433 −0.0568 −0.0708 Average −0.0206 −0.0383 −0.0561 −0.0735 −0.0911stdev 0.0040 0.0078 0.0118 0.0156 0.0191 rel stdv −19% −20% −21% −21%−21%

Note that the difference in mass released by rods D3 and D1 is initiallyas large as 50%, while the relative standard deviation is about 20%.

The release reproducibility obtained by loading rods with the procedureof Examples 1 and 2 is illustrated in Table 17, showing weight loss overtime for rods of paper from Plant D loaded with C12.

TABLE 17 hours 0.75 1.75 2.25 2.75 3.75 D1 −0.0400 −0.0932 −0.1004−0.1254 −0.1775 D2 −0.0334 −0.0766 −0.0876 −0.1079 −0.1491 D3 −0.0381−0.0810 −0.0924 −0.1122 −0.1537 Average −0.0372 −0.0836 −0.09347−0.11517 −0.1601 stdev 0.0034 0.0086 0.0065 0.0091 0.0152 rel stdv 9%10% 7% 8% 10%

The data shows a much tighter release, with differences between rodstypically less than 20%, and relative standard deviations typically 10%or less. We have observed this performance over a large number ofstudies.

Delivery rates. The rate of delivery data for rods of paper from Plant Dloaded with C12 by soaking is shown below for two time intervals, 1-2.5and 6.5-7.5 hours.

TABLE 18 SUMMARY OUTPUT DOMTAR C12, 1-2.5 hours Regression StatisticsMultiple R 0.999992 R Square 0.999983 Coefficients Standard ErrorIntercept −0.00322 0.000188 Loss, g/h −0.03517 0.000102 DOMTAR C12,6.5-7.5 hours Regression Statistics Multiple R 0.999936 R Square0.999873 Coefficients Standard Error Intercept 0.000322 0.003104 Loss,g/h −0.03923 0.000443

While probably not significant, the difference in rates between the twotime periods, −0.0352 and −0.0392 g/hour, may have been caused by thetime required to establish a steady-state equilibrium. Initially,towel-drying would disrupt the equilibrium at the rod surface, thus, thesteady state could have been reached after the first few hours. Thoserates are comparable to the −0.0391 g/hour reported for theVacuum/Pressure loaded rods. This likely means that, as long as the samematrix material is used, the rates are determined only by the amount offree liquid in the rods. For rods of paper from Plant D, the free liquidis close to the 70% of the load, as previously reported.

More interesting is the difference between the rods of paper from PlantD and rods of Type 2 paper from Plant G Data for rods of Type 2 paperfrom Plant G loaded by soaking in C12 are shown below in Table 19.

TABLE 19 SUMMARY OUTPUT Rods of Type 2 paper from Plant G C12, 1-2.5hours Regression Statistics Multiple R 0.999954 R Square 0.999907Coefficients Standard Error Intercept −0.0002 0.0003 Loss, g/h −0.024040.000164 Rods of Type 2 paper from Plant G C12, 6.5-7.5 RegressionStatistics Multiple R 0.999905 R Square 0.999811 Coefficients StandardError Intercept 0.004711 0.002564 Loss, g/h −0.02657 0.000366

The relative standard deviations of rods of paper from Plant D and rodsof Type 2 paper from Plant G loaded by soaking are comparable (about20%). Although we would expect a relatively large error in the deliveryrates as a consequence of the large standard deviations, the absoluterates between the two time periods are in close agreement, −0.0240 and−0.0266 g/hour. In spite of a much larger load (48% vs. 34% for rods ofpaper from Plant D), the rods of Type 2 paper from Plant G rates aresmaller than the −0.039 g/hour reported for rods of paper from Plant D.The lower rates attainable with the rods of Type 2 paper from Plant Gmaybe due to the paper's microstructure, and may achieve longer deliverytimes. See FIG. 6A.

The delivery of rods of paper from Plant D is linear for the first 15hours, but deviates from linearity (shown by the squares) around theexpected point, i.e., 70%. Thus, the line (small diamond) representingthe delivery rate of rods of paper from Plant D begins to flatten outafter about 15 hours: the slope changes from about 39 mg per hour forthe first ten hours to 7 mg per hour at 30 hours.

By contrast, the rods of Type 2 paper from Plant Gare still delivering aconstant rate at 30 hours: the slope a constant 26±1 mg over the 30 hourperiod shown below. Thus, while initially delivering a smaller amount ofmaterial per unit time to the environment, i.e., 26 vs. 39 mg/hour, therods of Type 2 paper from Plant Gdeliver that amount linearly over atime span twice as long as possible with the rods of paper from Plant D.See FIG. 6B.

The FIG. 6B shows weight loss vs. hours in the rapid release box forrods of Type 2 paper from Plant Gloaded with C12 by soaking. Over 70% ofthe mass loaded (0.9 g/1.22 g) is released to the air at a constant rateof 26 mg (0.026 g) per hour.

Example 8 Release Rates Using Krylon Clear Glaze 0500

Coatings were used to modulate delivery rates. Using rods of paper fromPlant D loaded with Douglas Fir and coating them with Krylon 0500,purchased commercially and available from Krylon Products Group,Cleveland Ohio. This coating is film-like, soft, and with no surfacediscontinuities apparent under microscopic inspection.

Procedure. Coating was done by fitting rods with caps, and suspendingthem on a horizontal rod. The rods were weighed prior to, and afterspraying. A five minute drying time in the Plexi-glass rapid-test box ofExample 3 was used before weighing. Five 9.5″ rods of paper from Plant Dloaded with Douglas Fir, and three 5.5″ rods of paper from Plant Gloaded with nC12, were sprayed with Krylon 0500 by moving the can acrossthe rods at a distance of about 10 inches. The rods were rotated 180degrees and the spraying repeated.Results. The coating of rods was done step-wise, and a decision tore-coat was made after measuring release rates. The initial results ofcoating 5.5″ rods of paper from Plant G loaded with C12 are shown belowin Table 21. To calculate rates, the average weight loss of three rodswas used.

TABLE 20 initial wgt 1 coat 0 1 2 2.5 9:00 AM 9:30 9:40 9:50 10:50 11:20AM AM AM AM AM K-G12-1 4.9395 4.9788 4.9782 4.9669 4.9225 4.9011 K-G12-24.9460 4.9828 4.9823 4.9728 4.9327 4.9135 K-G12-3 4.9271 4.9702 4.96924.9614 4.9318 4.9173 u-G12-4 4.8917 4.8917 4.8917 4.8847 4.8534 4.8370u-G12-5 4.9812 4.9812 4.9812 4.973 4.9334 4.9132 u-G12-6 4.9035 4.90354.9035 4.8963 4.8637 4.8464 K-G12-1 0.0393 −0.0113 −0.0557 −0.0771K-G12-2 0.0368 −0.0095 −0.0496 −0.0688 K-G12-3 0.0431 −0.0078 −0.0374−0.0519 u-G12-4 0 −0.0070 −0.0383 −0.0547 u-G12-5 0 −0.0082 −0.0478−0.0680 u-G12-6 0 −0.0072 −0.0398 −0.0571 ave K-G12 −0.0095 −0.0476−0.0659 stdv 0.0018 0.0093 0.0128 rel stdv −18% −20% −19% ave u-G12−0.0075 −0.0420 −0.0599 stdv 0.0006 0.0051 0.0071 rel stdv −9% −12% −12%ave K-G12 ave u-G12 hours loss, g calc hours loss, g calc 1 −0.0095−0.0096 1 −0.0075 −0.0074 2 −0.0476 −0.0473 2 −0.0420 −0.0423 2.5−0.0659 −0.0661 2.5 −0.0599 −0.0597 Multiple R 0.99996 Multiple R0.99995 Intercept 0.0280 Intercept 0.0275 Rate, g/H −0.0377 Rate g/H−0.0349

The average weight gain due to coating three rods of paper from Plant G,labeled K-G12-1 to 3, is about 0.040 g, as shown under the columnlabeled “1 coat” in the table above. The release rate was essentiallyunchanged by the coating: −0.0377 compared to −0.0349, and virtually thesame, −0.0387 g/H, as seen previously. Because the 40 mg coat did notchange the delivery rate, all the previously-coated rods were re-coated.

The second coat resulted in a weight gain of 56 and 57 mg for rodsK-G12-1 and 3, and 73 mg for K-G12-2. The uneven nature of the weightgain was due to experimental variables. The average release rate isshown below in Table 21.

TABLE 21 ave K-G12, 2 d coat, 9.5 H calc ave u-G12, 9.5 H calc 0.5−0.0136 −0.0126 0.5 −0.0198 −0.0200 1 −0.0249 −0.0225 1 −0.0392 −0.03941.5 −0.0338 −0.0325 1.5 −0.0590 −0.0589 2.5 −0.0508 −0.0525 2.5 −0.0980−0.0977 3.5 −0.0715 −0.0725 3.5 −0.1365 −0.1366 4.5 −0.0879 −0.0925 4.5−0.1759 −0.1755 8.5 −0.1734 −0.1724 8.5 −0.3306 −0.3309 9.5 −0.1940−0.1924 9.5 −0.3698 −0.3698 Multiple R 0.9994 Multiple R 1.0000Intercept −0.0026 Intercept −0.0006 Rate, g/H −0.0200 Rate, g/H −0.0389

The average rate for coated rods was about 50% lower (−0.0200 vs.−0.0389 g/H) than that for un-coated rods. In addition, both sets ofrods deliver their load linearly as shown by the best-fit straight-lineresults (Intercept+Rate×time in hours) shown under the column labeled“calc”. Thus, the second coating produced the desired rate reduction.

The uneven nature of the coating produced uneven delivery rates as shownby FIG. 7A showing individual weight loss from coated rods. Y is gramswt vs time in hours (X axis)

Note that for coated rod K-G12-1, abbreviated K1 in the graph (diamond),the release, while linear, is somewhat erratic when compared to rods 2(square) and 3 (triangles). The best-fit straight lines (calc K1-K3) arealso shown for reference. Note also that the rod with the heaviestcoating, K-G12-2 abbreviated K2-squares-in the graph, has the lowestrelease, 11.3 mg/H vs. 22.3 and 16.5 mg/H for K1 and K3. This is shownin Table 22.

TABLE 22 abbreviation K1 K2 K3 K-G12-1 K-G12-2 K-G12-3 Multiple R 0.99590.9991 0.9986 Intercept −0.0296 −0.0120 −0.0232 Rate g/H −0.0223 −0.0113−0.0165

A consequence of the variance with time was that the average rate overan extended period of time (48 hours) is slightly different from thatreported above for the period lasting 9.5 hours (−0.0200 vs. −0.0167g/H). Another possible explanation is that the coating, after 48 hours,has hardened some more thereby reducing the rate compared to the early(less hard) coat. The FIG. 7B shows the average loss over time comparedto the straight line fit obtained at 9.5 hours.

The load is 1.64 g per 5.5″ rods of paper from Plant G. As seen belowfor the uncoated rods (diamonds) about 1.2 g are delivered linearly, orabout 70% of the load, as previously reported for rods of paper fromPlant G. The coated rods showed deviations from linearity maybe due tothe lack of uniformity, or the changing nature of the Krylon coating asit cures over time. Nevertheless, it is clear that the coated rods werefar from exhausted when compared to the uncoated rods (50% of loaddelivered at 48 hours compared to 70% of the load at 30-35 hours).

The same approach was used to follow the coating of 9.5″ rods of paperfrom Plant D loaded with Douglas Fir.

Covering paper rods with a glossy coating, delivered by the use ofKrylon clear glaze, was a viable approach to modulate delivery rates.

1. A scented article, comprising, at least one olfactory-activecomposition, a structural component comprising an absorbent matrixmaterial, and a coating composition covering a portion of the structuralcomponent, wherein at least one olfactory-active composition isreleasably retained in the absorbent matrix material.
 2. The article ofclaim 1, wherein the absorbent matrix material is a pulp composition. 3.The article of claim 1, wherein the absorbent matrix material is a sheetof porous paper wound about a central axis to form a multilayered paperrod.
 4. The article of claim 3, wherein the wound paper forms a chamberthrough the central axis of the rod that is hollow and open at bothends.
 5. The article of claim 4, wherein the chamber formed along thecentral axis of the rod is filled with a gel or liquid.
 6. The articleof claim 1, wherein the absorbent matrix material has a void volume ofabout 1.0% to about 99% of the total volume of the structural component7. The article of claim 5, wherein the gel or liquid comprises at leastone olfactory-active composition.
 8. The article of claim 1, wherein thecoating covers more than 50% of the structural component.
 9. The articleof claim 1, wherein the coating covers substantially all of thestructural component.
 10. The article of claim 1, wherein the coatingcomposition comprises a wax, soy wax, paraffin, bees wax, polyethylenewax, microcrystalline wax, waxes that soften or melt at a temperaturegreater than about 150 F, acrylates,polylactide, polyglycolide orpolycaprolactone, or a polyester copolymer selected frompoly(lactide/glycolide) acid (PLGA) orpoly(lactid-co-.epsilon.-caprolact-one) (PLCL), alkyl- oralkoxyalkyl-2-cyanoacrylates such as n-butyl-2-cyanoacrylate or2-methoxybutyl-2-cyanoacrylate, crosslinked cyanoacrylate, polylacticacid, polyglycolic acid, lactic-glycolic acid copolymers,polycaprolactone, lactic acid-caprolactone copolymers,poly-3-hydroxybutyric acid, polyorthoesters, polyalkyl acrylates,copolymers of alkylacrylate and vinyl acetate, polyalkyl methacrylates,and copolymers of alkyl methacrylates and butadiene; and plasticizerssuch as dioctyl phthalate, dimethyl sebacate, trethyl phosphate, tri(2-ethylhexy) phosphate, tri(p-cresyl)phosphate, glyceryl triacetate,glyceryl tributyrate, diethyl sebacate, dioctyl adipate, isopropylmyristate, butyl stearate, lauric acid, dibutyl phthalate, trioctyltrimellitate, and dioctyl glutarate, Krylon® Triple-Thick crystal clearglaze.
 11. A method for making a scented article, comprising, a) addingat least one liquid olfactory-active composition and at least one matrixmaterial or at least one structural component, to a closed container;and in no particular order, b) applying a vacuum to the closed containerand maintaining the vacuum for a period of time before releasing thevacuum; and c) pressurizing the closed container and maintaining thepressure for a period of time before releasing the pressure.
 12. Themethod of claim 11, wherein steps b) and c) are repeated at least once.13. The method of claim 11, wherein applying a vacuum comprises a vacuumfrom about 0.001 mm Hg to about 700 mm Hg.
 14. The method of claim 11,wherein pressurizing the closed container comprises a pressure fromabout 10 psi to about 40 psi.
 15. The method of claim 11 wherein theperiod of time for the vacuum or the pressure is from 1 minute to 10hours.
 16. The method of claim 11, wherein the olfactory-activecomposition comprises at least one of a fragrance, repellant, odoreliminating compound, aromatherapy compound, natural oil, water-basedscent, odor neutralizing compound, or cyclodextrin.
 17. The method ofclaim 11, wherein a sufficient amount of an olfactory-active compositioncomprises an amount that covers substantially all of the at least onestructural component.
 18. The method of claim 11, further comprising d)removing the at least one matrix material or at least one structuralcomponent from the closed container.
 19. The method of claim 11, whereinthe structural component comprises a sheet of absorbent paper woundabout a central axis to form a multilayered paper rod.
 20. The method ofclaim 11, wherein the portion of the olfactory-active composition thatis absorbed by the structural component is from 2 to 200 mL.
 21. Amethod for making a scented article, comprising, a) adding at least oneliquid olfactory-active composition and at least one matrix material orat least one structural component to a closed container; and optionally,b) applying a vacuum to the closed container and maintaining the vacuumfor a period of time before releasing the vacuum; or c) pressurizing theclosed container and maintaining a pressure for a period of time beforereleasing the pressure.
 22. The method of claim 21, wherein step b) orstep c) is repeated at least once.
 23. The method of claims 21, whereinboth steps b) and c) are repeated at least once.
 24. The method of claim21, wherein a vacuum is applied.
 25. The method of claim 21, wherein apressure is applied.
 26. The method of claim 21, wherein a vacuum and apressure are applied.
 27. The method of claim 21, wherein applying avacuum comprises a vacuum from about 0.001 mm Hg to about 700 mm Hg. 28.The method of claim 21, wherein pressurizing the closed containercomprises a pressure from about 10 to about 40 psi.
 29. The method ofclaim 21, wherein the period of time for the vacuum or the pressure isfrom 1 minute to 10 hours.
 30. The method of claim 21, wherein theolfactory-active composition comprises at least one of a fragrance,repellant, odor eliminating compound, aromatherapy compound, naturaloil, water-based scent, odor neutralizing compound, or cyclodextrin. 31.The method of claim 21, wherein a sufficient amount of anolfactory-active composition comprises an amount that coverssubstantially all of the at least one structural component.
 32. Themethod of claim 21, further comprising f) removing the at least onematrix material or at least one structural component from the closedcontainer.
 33. The method of claim 21, wherein the structural componentcomprises a sheet of absorbent paper wound about a central axis to forma multilayered paper rod.
 34. The method of claim 21, wherein theportion of the olfactory-active composition that is absorbed by thestructural component is from 2 to 200 mL.
 35. A scented article,comprising, at least one olfactory-active composition, a structuralcomponent comprising a matrix material of extruded or molded pulpcomposition, wherein the at least one olfactory-active composition isreleasably retained in the absorbent material.
 36. The article of claim35, further comprising a coating covering a portion of the structuralcomponent.
 37. The article of claim 35, wherein the pulp compositionfurther comprises nanofibers.
 38. The article of claim 35, wherein thepulp composition is extruded.
 39. The article of claim 35, wherein thepulp composition is molded.
 40. The article of claim 35, wherein thepulp composition further comprises additives.